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PETROLEUM FILLING HISTORY OF CENTRAL ALASKAN NORTH SLOPE FIELDS

APPROVED BY SUPERVISORY COMMITTEE:

_______________________________________ Richard M. Mitterer, Chair

_______________________________________ Janok P. Bhattacharya

_______________________________________ Albert G. Holba

_______________________________________ James L. Carter

_______________________________________ Kent C. Nielsen

This dissertation is dedicated to Coleen and our children: Dallam, Joseph, Kathleen, Anthony, James, and Mark

PETROLEUM FILLING HISTORY OF CENTRAL ALASKAN NORTH SLOPE FIELDS

by

Wilmer Dallam Masterson IV, B.S., M.A.

DISSERTATION Presented to the Faculty of The University of Texas at Dallas in Partial Fulfillment of the Requirements for the Degree of

DOCTOR OF PHILOSOPHY IN GEOSCIENCES

THE UNIVERSITY OF TEXAS AT DALLAS May, 2001

PREFACE This dissertation was produced in accordance with guidelines which permit the inclusion as part of the dissertation the text of an original paper, or papers, submitted for publication. The dissertation must still conform to all other requirements explained in the "Guide for the Preparation of Master's Theses, Doctoral Dissertations, and Doctor of Chemistry Practica Reports at The University of Texas at Dallas." It must include a comprehensive abstract, a full introduction and literature review, and a final overall conclusion. Additional material (procedural and design data as well as descriptions of equipment) must be provided in sufficient detail to allow a clear and precise judgment to be made of the importance and originality of the research reported. It is acceptable for this dissertation to include as chapters authentic copies of papers already published, provided these meet type size, margin, and legibility requirements. In such cases, connecting texts which provide logical bridges between different manuscripts are mandatory. Where the student is not the sole author of a manuscript, the student is required to make an explicit statement in the introductory material to that manuscript describing the student's contribution to the work and acknowledging the contribution of the other author(s). The signatures of the Supervising Committee which precede all other material in the dissertation attest to the accuracy of this statement. The geochemical research for this dissertation was begun at ARCO Exploration and Technology Company in Plano, Texas, and was completed at ARCO Alaska, Inc. and Phillips Alaska, Inc. in Anchorage, Alaska. This dissertation builds upon research by Albert Holba and Leon Dzou, who pioneered the use of modern geochemical technologies to unravel the composition of North Slope oil mixtures. I am indebted to them for their encouragement and for their continued support and constructive criticism. The proprietary GENESIS and EXODUS basin models used in this study were written by Zhiyong He and others at ARCO. Many other co-workers at ARCO have contributed to the study of Alaskan North Slope petroleum systems over a number of years. I particularly wish to acknowledge the contributions of Susan Singletary, Ann Fincannon, and Leroy Ellis for GC/MS/MS and GC/IRMS analyses; Lee Lundell and Mark McCaffrey for their geochemical insights regarding the North Slope petroleum system; Alton Brown for his tireless reviews of earlier versions of parts of the manuscript; Jeff Corrigan for construction of the initial GENESIS 1D models of wells in the area; John Bennett for palynological analyses and interpretations; Eric Tegelaar for studies of North Slope source rock kinetics; Mike Werner, Chip Landmesser, Diane Shellenbaum, and Tom Eggert for their knowledge of the West Sak Field; and Steve Benzler and Ken Nelson for mapping and graphical support. I also acknowledge the support of the Prudhoe Bay, Kuparuk River, and Colville River Unit Working Interest Owners and am grateful to Phillips Alaska, Inc., BP Exploration (Alaska), and Anadarko Petroleum Company for permission to publish. The conclusions expressed in this dissertation are mine and are not necessarily shared by the Working Interest Owners. January, 2001

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PETROLEUM FILLING HISTORY OF CENTRAL ALASKAN NORTH SLOPE FIELDS Publication No.__________ Wilmer Dallam Masterson IV, Ph.D. The University of Texas at Dallas, 2001 Supervising Professor: Richard M. Mitterer

The petroleum filling history of the central Alaskan North Slope was reconstructed with burial history models that were calibrated with source rock and oil geochemistry in the area surrounding the Prudhoe Bay, Kuparuk, West Sak, Pt. McIntyre, Tarn, and Alpine Fields. Prudhoe Bay and Kuparuk are the two largest currently producing oil fields in the United States. Oil in the Prudhoe Bay Field is interpreted as a mixture co-sourced from three source rocks: Upper Triassic marine carbonate, shale, and phosphorite (Shublik Formation), Lower Cretaceous marine shale (HRZ Formation), and Lower Jurassic marine shale (Kingak Shale). The total expelled oil volume within the Prudhoe Bay Field fetch area of 4,000 square miles is modeled to be 168 billion barrels and consists of 59% Shublik, 28% HRZ, and 13% Kingak source rock contribution. The carbon isotopic composition, API gravity, and sulfur content of the Prudhoe Bay main field oil accumulation closely match the modeled oil composition in the Prudhoe Bay fetch area. The estimated 40 to 50 billion barrels of original oil in place in the Prudhoe Bay and West Sak Fields imply a Prudhoe Bay fetch area migration efficiency of 25 to 30%. Spillage of Prudhoe oil into the West Sak Field occurred during post-Eocene uplift and 1-2 degrees of eastward tilting that decreased the hydrocarbon column at Prudhoe Bay Field from 2400 to 1000 feet and created the structural trap at the Prudhoe Bay West End. The Prudhoe Bay main field tar mat formed when gas deasphalted the oil column in Tertiary time, and carbonates in the Carboniferous Lisburne Formation are interpreted as the source of most of the carbon dioxide in the Prudhoe Bay gas cap. Kuparuk Field oils were predominantly sourced from Shublik source rock. The HRZ Formation is interpreted as the primary source for Tarn Field oils and the Kingak Shale is interpreted as the primary source for Alpine Field oils. The West Sak Field accumulation is interpreted as a mixture of moderately biodegraded oil that spilled from the Prudhoe Bay Field and lightly biodegraded gas/condensate that leaked from the underlying Kuparuk Field.

TABLE OF CONTENTS

Dedication Preface. Abstract List of Tables... List of Figures.. General Introduction Chapter 1. Origin of Oils and Gases... Introduction. Synopsis.. Geological Setting... Methods... Geochemical Evaluation of Potential Source Rocks... Shublik Formation... Kingak Shale... HRZ Formation... Other Potential Source Rocks. Origin of Oils.. Kuparuk and Alpine Fields. Tarn Field and Other Oils Sourced from Cretaceous Rocks.. Prudhoe Bay Main Field. Prudhoe Bay Main Field Tar Mat... Prudhoe Bay Field West End.. Point McIntyre Field... West Sak Field Origin of Gases............................................................................................... Interpreted End-Member Gases from a Single Source... West Sak Field Prudhoe Bay Field.. Point McIntyre Field... Kuparuk Field. Tarn and Alpine Fields... Conclusions. Chapter 2. Evidence for Biodegradation and Evaporative Fractionation in West Sak, Kuparuk, and Prudhoe Bay Field Areas........................................................................... Introduction........................................................................................................... Synopsis.............................................................................................................

ii iv vi x xi 1 4 4 5 6 14 14 14 18 19 21 22 22 27 29 32 34 36 37 39 39 41 41 46 48 50 51 54 54 55

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Geological Setting.......................................................................................... Methods......................................................................................... Samples.. Sample Preparation Whole Oil Gas Chromatography (GC).. Gas Chromatography-Mass Spectrometry (GC/MS). Gas Chromatography-Mass Spectrometry-Mass Spectrometry (GC/MS/MS). Gas Chromatography-Isotope Ratio Mass Spectrometry (GC/IRMS).. Oil-Source Rock Correlation. Evidence for Biodegradation of West Sak Field Oils and Gases.. Source of West Sak Light Hydrocarbons... Loss of Light Hydrocarbons from Kuparuk Oils by Evaporative Fractionation... Isotopic Evidence for Evaporative Fractionation of Kuparuk Oils........... Mechanism for Gas Leakage from Kuparuk Field Implications for Development of West Sak Oil Reserves..................................... Conclusions.......................................................................................................

57 60 60 61 62 62 62 63 64 67 79 83 85 89 91 92

Chapter 3. Burial History Models..................................................................................... 94 Introduction........................................................................................................... 94 Synopsis............................................................................................................ 95 Methods......................................................................................... 97 Source Rock Analyses... 97 Burial History Models... 98 Kinetic Models for Hydrocarbon Generation 104 Petroleum Filling Histories... 110 Lower Cretaceous Unconformity.. 110 Late Cretaceous (66 Ma) Reconstruction.. 111 Middle Eocene (45 Ma) Reconstruction.... 113 Present Day 117 Sensitivities to Burial History Model Parameters. 123 Migration Efficiency and Carrier Beds. 125 Conclusions....................................................................................................... 129 References............................. 132 Tables 146 Figures... 162 Vita

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LIST OF TABLES Table Page 1.1 Rock Eval data for source rocks 146 1.2 1.3 1.4 1.5 2.1 2.2 2.3 2.4 2.5 2.6 3.1 3.2 3.3 Carbon isotope, GC, GC/MS, and GC/MS/MS data for source rocks.. 147 Geochemical data for North Slope oils.. 149 Average concentrations of biomarkers in core extracts (ppm).. 152 Average chemical and isotopic composition of selected North Slope gases. 153 West Sak, Kuparuk, and Prudhoe Bay Field oils analyzed by GC/IRMS. 154 GC/IRMS carbon isotopic compositions of selected C6 and C7 compounds in oils.. 155 Concentrations of selected C6 and C7 compounds in West Sak and Kuparuk oils 156 Condensate-range maturity parameters in West Sak and Prudhoe Bay oils.. 157 Data from Kuparuk Field bottomhole oil samples.158 Calculation of inferred isotopic fractionation factor between Kuparuk residual oil and West Sak secondary gas/condensate charge... 159 Source rock geochemical parameters used in EXODUS model 159 Kinetic parameters for source rocks.. 160 Comparison of EXODUS model predictions with Prudhoe Bay main field oil compositions.. 161

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LIST OF FIGURES Figure Page 1.1 Location of oil fields on the North Slope of Alaska. 162 1.2 Generalized structural cross section from the Brooks Range across the North Slope to the Beaufort Sea.. 163 Generalized stratigraphic column for the Prudhoe Bay/Kuparuk River area of the Alaskan North Slope 164 Structural cross section through Kuparuk, West Sak, and Prudhoe Bay Fields 165 Wireline log response and organic richness of source intervals in the HRZ Formation, Kingak Shale, and Shublik Formation 166 Locations of oil samples, source rock samples, and producing units 167 Rock Eval data from Shublik, Kingak, and HRZ cores. 168 GC/MS saturate fraction mass chromatogram (m/z 191) of source rock extracts and oils sourced from the Kingak Shale and from shaly and calcareous facies of the Shublik Formation.. 169 Source-diagnostic compounds in Kuparuk and Prudhoe Bay Field oils compared to Shublik, Kingak, and HRZ source intervals. 170

1.3

1.4 1.5

1.6 1.7 1.8

1.9

1.10 Carbon isotopic composition of saturated and aromatic compounds extracted from cores through the Shublik, Kingak, and HRZ source intervals 171 1.11 GC/MS/MS saturate fraction mass chromatogram (m/z 358? ?? 217 transition) of HRZ, Kingak, and Shublik source rocks and oils from Prudhoe Bay, West Sak, and Tarn Fields.. 172 1.12 Carbon isotopic composition of saturated and aromatic compounds in crude oils.. 173 1.13 Source-diagnostic compounds in Kingak-sourced oils compared to Shublik and Kingak source rocks. 174 1.14 Prediction of API gravity from biomarker ratios in oils sourced from the Shublik Formation and the Kingak Shale in the Colville Delta area 175 1.15 Source-diagnostic compounds in Umiat, Tarn, and Kuukpik #3 oils 176 1.16 API gravity and sulfur content of oils in the study area 177 1.17 Biomarker and isotopic evidence for mixed oils in the Prudhoe/Kuparuk area 178

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1.18 Carbon isotopic composition of saturated and aromatic compounds extracted from Ivishak Sandstone cores in the Prudhoe Bay Field.. 179 1.19 Evidence for gravity segregation in the Prudhoe Bay main field oil column above the tar mat.. 180 1.20 Concentration and isotopic composition of carbon dioxide in separator gas from the Pt. McIntyre Field.. 181 1.21 Whole oil gas chromatograms (GC) and GC/MS saturate fraction mass chromatograms (m/z 191) of oils from the Kalubik #1 and the West Sak, Kuparuk, and Prudhoe Bay Fields 182 1.22 Natural gas plot (Chung et al., 1988) showing carbon isotopic compositions of gases and interpreted range of Shublik-sourced gases. 183 1.23 Wetness and methane carbon isotopic composition of gases interpreted as sourced from the Shublik Formation (Kalubik #1) and the Lisburne Formation (2F-20). 184 1.24 Carbon and hydrogen isotopic compositions of methane from the Kalubik #1 and 2F-20 wells. 185 1.25 Maturity of gases in the Kalubik #1 and 2F-20 wells, using the method of James (1990). 186 1.26 Average concentration and carbon isotopic composition of carbon dioxide in gases. 187 2.1 Locations of oil samples, source rock samples, and north/northeast-striking faults of Tertiary age that displace the top of the Kuparuk River Formation.. 188 Schematic structural cross section illustrating filling history of West Sak Field.. 189 GC/IRMS whole oil mass chromatogram (m/z 44) of Kuparuk zone A oil from the KRU 1E-11 well. 190 GC/MS saturate fraction mass chromatogram (m/z 191) of extracts from Shublik, Kingak, and HRZ source rocks.. 191 Whole oil gas chromatograms (a, b, and c) and GC/MS saturate fraction mass chromatograms (m/z 191; d, e, and f) of oils from the West Sak, Kuparuk, and Prudhoe Bay Fields... 192 The isotopic compositions of West Sak methane, carbon dioxide, and

2.2

2.3

2.4 2.5

2.6

formation water suggest that methane was generated by CO2 reduction in an anaerobic environment. 193 2.7 Carbon isotopic compositions of solution gas from West Sak and Kuparuk Fields. 194 Wireline logs and whole oil gas chromatograms from the West Sak reservoir at the WSP 8I well. 195 Concentrations of selected compounds in oils from West Sak and Kuparuk Fields. 196

2.8

2.9

2.10 Carbon isotopic composition of oils from the West Sak reservoir in the WSP 8I well (a) and the WS 1-01 well (b)... 197 2.11 Carbon isotopic composition of West Sak oils in zones A and B 198 2.12 Wireline logs and permeabilities measured from cores through the West Sak reservoir in the WS 1-01 well... 199 2.13 Comparison of carbon isotopic compositions in West Sak zone A and Kuparuk oils (a) and Prudhoe Ivishak oils (b).. 200 2.14 Evidence for evaporative fractionation in Kuparuk Field oils and simplified structure map (feet subsea) on the top of Unit A, Kuparuk Formation. 201 2.15 Comparison of n-alkane molar fractions in Kuparuk and Prudhoe Bay Field oils. 202 3.1 3.2 3.3 3.4 3.5 Location of modeled wells on the North Slope of Alaska 203 Burial history model of the Phoenix #1 well 204 Burial history model of the Bush Federal #1 well 205 Isopach and structure maps used in the EXODUS model. 206 Rock Eval S1 and TOC (total organic carbon) measurements on cores from HRZ, Kingak, and Shublik source rocks.. 207 Isopach maps of HRZ, Kingak, and Shublik source rocks 208 Temperature gradient across Prudhoe Bay main field at 8800 feet subsea depth. 209 Rock Eval Tmax and Production Index (S1/(S1 + S2)) measurements on source rock cores.. 210

3.6 3.7 3.8

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3.9

Comparison between modeled and measured vitrinite reflectances. 211

3.10 Modeled source rock transformation ratios as a function of temperature at a heating rate of 10C/my 212 3.11 Modeled rate of hydrocarbon generation from calcareous facies of the Shublik Formation at the Bush Federal #1 well. 213 3.12 Reconstructed structural cross section through Kuparuk and Prudhoe Bay Fields during development of the Lower Cretaceous Unconformity (LCU) in Early Cretaceous time (125 Ma). 214 3.13 Reconstructed structural cross section through Kuparuk and Prudhoe Bay Fields during Late Cretaceous time (66 Ma). 215 3.14 Distribution of subsurface faults mapped from seismic data in the Prudhoe Bay/Kuparuk Field area. 216 3.15 Isopach maps of Paleocene and Maastrichtian/Campanian sediments. 217 3.16 EXODUS models of hydrocarbon kitchens in Late Cretaceous time (66 Ma). 218 3.17 Reconstructed structural cross section through Kuparuk and Prudhoe Bay Fields during Late Eocene time (40 Ma), after the onset of Tertiary uplift and eastward tilting.. 219 3.18 EXODUS models of hydrocarbon kitchens in Middle Eocene time (45 Ma). 220 3.19 EXODUS modeled area of CO2 generation from the Lisburne Group in Middle Eocene time (45 Ma) 221 3.20 EXODUS models of present-day hydrocarbon kitchens. 222

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GENERAL INTRODUCTION The petroleum sources and filling histories of the oil fields on the central Alaskan North Slope have been debated since discovery of the Prudhoe Bay Field in 1967 and the Kuparuk and West Sak Fields in 1969. Part of the uncertainty arose from the recognition in the late 1970s that Prudhoe Bay Field oil is a mixture co-sourced from at least two source rocks. Recent advances in geochemical analytical techniques and basin models have created new tools to determine the relative contributions of each of the North Slope source rocks to the Prudhoe Bay, Kuparuk, West Sak, Pt. McIntyre, Tarn, and Alpine Fields. The origins of central Alaskan North Slope oils and gases are discussed in Chapter 1, the origins of biodegraded oils and condensate-range compounds at the West Sak Field are discussed in Chapter 2, and the burial history models and filling histories of the fields are discussed in Chapter 3. Discovery of more than a billion barrels of additional recoverable oil reserves in new fields over the past decade has demonstrated that an understanding of the North Slope petroleum system remains of economic interest to the oil industry and to the United States. Many of the conclusions expressed in this dissertation are derived from the interpretation of biomarker and stable isotopic compositions of hydrocarbons in the crude oils. Biomarkers are compounds that were originally present in living organisms and were subsequently altered during source rock deposition, mineralization, diagenesis, hydrocarbon generation, and migration to form compounds in crude oils that retain the characteristic chemical structure of the precursor organism. For instance, cholestane is a sterane that is typically found in oils in small concentrations (parts per million) and is derived from cholesterol, a four-ringed steroid commonly found in living organisms (Peters and Moldowen, 1993). Biomarkers can be used to correlate oils with source rocks and can be used to interpret the environment of deposition, maturity, and, in some cases, the geologic age of the source rocks (Peters and Moldowen, 1993; Holba et al., 1998). Biomarkers provide a powerful tool to identify the co-sources of mixed crude oils in petroleum systems like the North Slope of Alaska that have several source rock intervals with distinctive biomarker signatures. However, because they are usually found only in trace quantities in oils and source rocks, care must be taken to avoid sources of contamination during sample preparation and analyses. Biomarkers typically contain more than 20 carbon atoms and are therefore useful in interpreting the origin of the liquid, or "black oil," fraction of petroleum, but do not necessarily indicate the origin of light gases and condensate-range compounds in the oil that could have been derived from other sources. Stable isotopes provide another tool to correlate oils with source rocks and are the only geochemical tool other than molar compositions that can be used to determine the source and maturity of light hydrocarbon gases. Isotopes are atoms with the same number of protons, but different numbers of neutrons. Unlike the carbon-14 (14C) radioactive isotope, the 13C stable isotope of carbon does not undergo radioactive decay and is present in varying concentrations in oils and gases due to the original ratio of 13C/12C in the source rocks and to thermodynamic and kinetic fractionation of hydrocarbons during petroleum generation, phase separation, biodegradation, and other processes that fractionate hydrocarbons due to differences in molecular mass (Galimov, 1973, 1980; Stahl, 1977, 1980). Deuterium (D or 2H), the stable isotope of hydrogen, is also useful in interpreting the origin of light hydrocarbon gases such as methane.

2 Stable isotopic compositions are reported relative to a standard using the ("delta") notation, which represents the deviation from a standard value in parts per million (, per mil) = (Rsample - Rstandard)/Rstandard x 1000 where R is the isotopic ratio, i. e. 13C/12C or D/H. A negative, or "isotopically light" -value indicates that the sample is enriched in the light isotope relative to the standard, and a positive or "isotopically heavy" value indicates that the sample is enriched in the heavy isotope relative to the standard. The standards used in this dissertation are PDB (a belemnite from the Cretaceous Peedee Formation) for carbon and Standard Mean Ocean Water (SMOW) for hydrogen. In Chapter 2, biomarkers and carbon isotopic compositions of condensate-range compounds are interpreted to indicate that oil in the West Sak Field is a mixture consisting of a moderately biodegraded oil from one source and a secondary gas/condensate charge from another source. To my knowledge, this is the first time that these geochemical techniques have been used to demonstrate different sources for the condensate-range and heavier components of a biodegraded oil.

CHAPTER ONE ORIGIN OF OILS AND GASES INTRODUCTION The origin of oils and gases on the central Alaskan North Slope has been previously discussed in numerous publications. The research reported in this dissertation builds upon years of work at the ARCO research lab and was initially conducted in collaboration with Albert Holba and Leon Dzou. At the time that this dissertation was initiated, Drs. Holba and Dzou had already recognized the distinctive biomarker signatures of the three major North Slope source rocks and had begun to unravel the origin of mixed oils in the study area. Several proprietary internal ARCO North Slope reports from 1994-1996 were co-authored by Holba, Dzou, Masterson, and others. In addition to these collaborative studies, this chapter presents the results of later research conducted solely by the author that include the biomarker signature of the calcareous Shublik source rock facies at the Phoenix #1 well and its correlation to Kuparuk Field and other North Slope oils, evidence for Kingak co-source of Prudhoe Bay and Kuparuk Field oils, the origin of oil accumulations near the West End of the Prudhoe Bay Field, a new methodology for determining the relative co-source proportions of Shublik and Kingak source rocks to oils in the Colville Delta area, the origin of gases at all of the fields, and the geological framework of the North Slope petroleum system. SYNOPSIS The origin of oils and gases on the central Alaskan North Slope was assessed with source rock geochemistry and migrated hydrocarbon compositions in the areas surrounding the Prudhoe Bay, Kuparuk, West Sak, Pt. McIntyre, Tarn, and Alpine Fields. Source-diagnostic biomarkers suggest that oil in the Prudhoe Bay Field is a mixture co-sourced from three source rocks: Upper Triassic marine carbonate, shale, and phosphorite (Shublik Formation), Lower Cretaceous marine shale (HRZ Formation), and Lower Jurassic marine shale (Kingak Shale). Isotopic and biomarker evidence suggests that an initial charge of Shublik, Kingak, and HRZ-sourced oil to the Prudhoe trap preceded a mixed gas charge. Oils in Upper Triassic Sag River sandstone reservoirs at the Prudhoe Bay West End are interpreted as mixtures co-sourced from the Shublik Formation and the Kingak Shale that directly underlie and overlie the Sag reservoir. The Prudhoe Bay main field gas cap is interpreted as a mixture sourced primarily from the Shublik Formation and the Carboniferous Lisburne Group, with possible additional gas charge from the HRZ Formation, Kingak Shale, and Mississippian Kekiktuk coals. An estimated 70% of the 5 trillion cubic feet (TCF) of carbon dioxide in the Prudhoe main field gas cap could have been derived from decarbonation of Lisburne Group carbonates. The Lisburne Group is also interpreted as a co-source for the carbon dioxide in the Pt. McIntyre and Prudhoe Bay Lisburne pool gas caps. Kuparuk Field oils were predominantly sourced from Shublik source rock. West Sak Field oils are a mixture of moderately biodegraded oil spilled from the Prudhoe Bay Field into Upper Cretaceous West Sak sandstones, and a lightly biodegraded secondary gas/condensate charge that leaked from the underlying Kuparuk Field. The presence of C29 25-norhopanes suggests that the Prudhoe Bay and Kuparuk oil accumulations were biodegraded in their early filling histories.

4 The HRZ Formation is interpreted as the primary source for Tarn Field oils and the Kingak Shale is interpreted as the primary source for Alpine Field oils. Shublik-sourced gas may also be present in both Tarn and Alpine Fields. Tarn and Alpine oil gravities range from 35 to 40 degrees API with sulfur concentrations of less than 0.3%, significantly different than the 20 to 30 degree API gravity range and ? 1% sulfur concentration in Kuparuk Field and Prudhoe Bay main field oils. The carbonate-rich Shublik source facies accounts for the lower API gravity and higher sulfur content of Prudhoe Bay and Kuparuk Field oils relative to Tarn and Alpine oils. The 1% average sulfur content of Prudhoe Bay main field oils suggests approximately 60% Shublik cosource and 40% HRZ and Kingak co-sources. GEOLOGICAL SETTING The Prudhoe Bay, Kuparuk, West Sak, Pt. McIntyre, Tarn, and Alpine Fields are located about 250 miles (400 kilometers) north of the Arctic Circle on the coastal plain of the North Slope of Alaska between the NPRA (National Petroleum Reserve, Alaska) and the ANWR (Arctic National Wildlife Refuge; Figure 1.1). The geologic settings for these fields have been previously described by Jones and Spears (1976), Jamison et al. (1980), Carman and Hardwick (1983), Masterson and Paris (1987), Werner (1987), and Masterson and Eggert (1992). The fields are located on a subsurface structural high known as the Barrow Arch, which parallels the Arctic coastline from Point Barrow to Prudhoe Bay (Figure 1.2; Bird and Bader, 1987). Reservoirs in the central Alaskan North Slope fields are found in three genetically unrelated stratigraphic sequences. The older Ellesmerian sequence consists of predominantly siliciclastic rocks of Late Devonian to Early Cretaceous age that overlie deformed Franklinian sequence argillite of Ordovician and Silurian age (Lerand, 1973; Carter and Laufeld, 1975; Figure 1.3). The provenance area for Ellesmerian sediments was to the north of the present-day coastline, probably in the Canadian Arctic Islands (Embry and Dixon, 1994). From Carboniferous to Early Cretaceous time, the Ellesmerian stratigraphic sequence was deposited during repeated transgressions and gradual onlap of its source terrain to the north. Endicott Group sediments at the base of the sequence include the Mississippian coals and fluvial sandstones of the Kekiktuk Formation that are the reservoir at the Endicott field east of Prudhoe Bay (Figures 1.1 and 1.3; Woidneck et al., 1987; Wicks et al., 1991). The Kekiktuk sandstone and overlying Kayak/Itkilyariak Formations grade conformably upward into the overlying Lisburne Group carbonates. Lisburne shallow marine platform oolitic grainstone, wackestone, dolomite, and shales of Mississippian and Pennsylvanian age host the subsidiary Lisburne Pool accumulation beneath the main Ivishak sandstone reservoir in the Prudhoe Bay Unit (Bird and Jordan, 1977; Jamison et al., 1980; Jameson, 1994). Lisburne Group carbonate rocks are unconformably overlain by siliciclastic sedimentary rocks of the Permian-Triassic Sadlerochit Group (Leffingwell, 1919; Detterman et al., 1975). Magnetostratigraphic correlations reported by Lawton et al. (1987) and paleontologic data in Detterman et al. (1975) indicate an Early Triassic age for the Ivishak Sandstone member of the Sadlerochit Group. The thickness of the Ivishak Sandstone reservoir at Prudhoe Bay Field varies from 650 feet (200 meters) in the southeast to about 325 feet (100 meters) in the northwest due to depositional thinning and to truncation by the Pre-Shublik Unconformity (Jones and Spears, 1976; Jamison et al., 1980; Lawton et al., 1987). The Ivishak Sandstone is divided into four

5 petrophysically defined zones that broadly correspond to sandy delta-front, distributary-mouth bar and distributary-channel facies (zone 1), sandy and pebbly braided fluvial channels, floodplain, and overbank deposits (zone 2), conglomeratic braided stream channel deposits (zone 3), and sandy braided stream deposits (zone 4; Wadman et al., 1979; Atkinson et al., 1990; Lawton et al., 1987; Tye et al., 1999). The Prudhoe Bay Field is the largest oil field in the United States, with 25 billion stock tank barrels (4 billion cubic meters) of original oil in place and 46 trillion standard cubic feet (1.3 trillion cubic meters) of gas in place in the original gas cap and in solution with the oil (BP and ARCO, 1997). It is about 30 miles long by 10 miles wide (50 km by 16 km) and the average depth of the Ivishak sandstone reservoir is about 8,800 feet (2,700 meters) subsea. The field produced at an average rate of about 550,000 barrels of oil per day (BOPD; 87,000 cubic meters per day) in 1999 and ultimate recoverable reserves are expected to exceed 13 billion barrels (2 billion cubic meters; BP and ARCO, 1997). The underlying Lisburne pool shares approximately the same fluid contacts as the Ivishak reservoir (Figure 1.4) but contains only an estimated 1 billion barrels (160 million cubic meters) of oil in place, 157 million barrels (25 million cubic meters) of which is recoverable (BP and ARCO, 1997; Alaska Oil and Gas Conservation Commission, 1999) The Shublik Formation that unconformably overlies the Ivishak Sandstone is a prolific North Slope source rock (Magoon and Bird, 1985). It is lithologically heterogeneous, but typically consists of two cycles within an overall transgressive sequence: a Middle Triassic basal sandstone or siltstone that grades upward into fossiliferous Upper Triassic limestone or calcareous shale (zone C), with increasing phosphate and glauconite towards the top (zone B); and an upper Norian cycle of mudstone grading upwards into calcareous siltstone or limestone (zone A; Bird, 1985; Kupecz, 1995; Hulm, 1999; Figure 1.5). The Shublik Formation is believed to have been deposited in an upwelling zone at a paleolatitude of about 50N, and becomes increasingly diluted with siliciclastic sediment towards a shoreline to the north (Parrish, 1987; Kupecz, 1995). The regressive Sag River Sandstone of Late Triassic to Early Jurassic age conformably overlies the Shublik Formation (Jones and Spears, 1976), and is a silty, very fine to fine-grained, glauconitic, bioturbated shallow marine sandstone. Sag River Sandstone permeabilities and porosities are relatively low compared to the Ivishak Sandstone and the Sag thins southward from 60 feet (18 meters) to zero thickness at the southern margin of the Prudhoe Bay Field (Barnes, 1987). Cuttings samples from wells in the southern part of the study area are sandy in the interval above the Shublik Formation, and the Sag time-equivalent interval could serve as a carrier bed for hydrocarbons generated to the south even though high-quality Sag reservoir rock does not extend south of the Prudhoe Bay Field. The Sag River reservoir contributes an estimated 4 billion barrels (635 million cubic meters) of oil and oil-equivalent gas to the Prudhoe Bay Field total hydrocarbons in place (Barnes, 1987). Sag River Sandstone is overlain disconformably by Kingak Shale, which ranges in age from Early Jurassic to Early Cretaceous (Detterman et al., 1975). Kingak Shale thickness varies from about 2000 feet (600 meters) between the Kuparuk and Prudhoe fields to zero thickness on the eastern side of Prudhoe Bay Field, where the Kingak and Shublik Formations have been eroded

6 beneath the Lower Cretaceous unconformity (LCU; Figure 1.4). The Kingak Shale is an adequate to good source rock, mainly in its basal interval (Figure 1.5) and has been cited as a minor source of North Slope oil (Magoon and Claypool, 1984). The Jurassic Kingak Shale is predominantly mudstone except in the western part of the study area where an Upper Jurassic marine sandstone is the reservoir at the Alpine Field (Figures 1.1, 1.3). The Alpine Field is a stratigraphic trap at about 7,000 feet (2,100 meters) subsea depth and contains 439 million barrels (70 million cubic meters) of recoverable reserves out of an estimated 1 billion barrels (160 million cubic meters) of oil in place (Hannon et al., 2000). Oil produced from the Alpine Field averages 400 API gravity, significantly lighter than oils from the Prudhoe Bay and Kuparuk Fields. In Early Cretaceous time, the North Slope rifted away from its northern source terrain in presentday Arctic Canada to form the Beaufort Sea, and the Kuparuk River Formation of the Beaufortian sequence was deposited during a period of tectonism characterized by uplift and formation of northwest-striking faults in the Kuparuk/Prudhoe Bay area (Halgedahl and Jarrard, 1987; Masterson and Paris, 1987; Figures 1.2, 1.3). Hubbard et al. (1987) also include the Jurassic Kingak Shale in the Beaufortian sequence, and rifting may have begun in Middle Jurassic time (Embry and Dixon, 1994). The Kuparuk River Formation is divided into two members that are separated by the LCU (Masterson and Eggert, 1992). The lower member consists of interbedded marine sandstone, siltstone and mudstone units of Berriasian (?) to Valanginian age. The lower member is divided into units A and B. The Kuparuk upper member overlies the LCU and contains more glauconite and siderite than the lower member. The upper member is divided into units C and D, which are composed of a sequence of bioturbated marine sandstone, siltstone, and mudstone deposited during Hauterivian to Barremian time. Sandstone and conglomerate of the Put River Sandstone (Jamison et al., 1980) were deposited in incised valleys at the future site of the Prudhoe Bay Field at about the same time as deposition of the Kuparuk upper member (Figure 1.4). The Kuparuk upper member is disconformably overlain by Kalubik mudstones at the Kuparuk Field, which separate the overlying HRZ source rock from the Kuparuk reservoir sandstones (Carman and Hardwick, 1983). The Kuparuk Field is a combination structural and stratigraphic trap at about 6,000 feet (1,825 meters) subsea depth (Masterson and Eggert, 1992). It produced at an average rate of 230,000 BOPD ( 37,000 cubic meters per day) in 1999, making it the second most productive field in the United States after the Prudhoe Bay Field. The Kuparuk Field covers an area of about 265 square miles (675 square kilometers) immediately west of Prudhoe Bay Field and originally held 6 billion stock tank barrels (950 million cubic meters) of oil in place (BP and ARCO, 1997). The Kuparuk Field had no gas cap and the oil was about 200 pounds per square inch (psi; 1,375 kilopascals) undersaturated with gas when it was discovered. Kuparuk Field reservoir thickness averages 30 feet (10 meters), significantly less than the Ivishak reservoir at Prudhoe Bay Field. The Kuparuk Formation is also the reservoir at the Point McIntyre Field, which is located 7 miles (11 km) north of the Prudhoe Bay Field along the western shoreline of Prudhoe Bay and is estimated to contain 800 million barrels (125 million cubic meters) of oil in place (Figure 1.1; BP and ARCO, 1997). The Kuparuk reservoir at Point McIntyre Field reaches up to 600 feet (180 meters) thickness along the downthrown sides of east-striking normal faults that form the

7 northern boundary of the Prudhoe Bay Field. Average reservoir depth at Point McIntyre is 8,800 feet (2,680 meters) and there is a small gas cap at the field (BP and ARCO, 1997). The HRZ (i. e., Highly Radioactive Zone; Carman and Hardwick, 1983) source rock unit of the Hue Shale (Molenaar et al., 1987) was deposited in water depths greater than 1,000 feet (300 meters) in the starved basin that formed as the North Slope rifted away from its northern source terrain at a paleolatitude of about 80N. It is the distal, basin plain facies of an Albian deltaic system that prograded from west to east in the NPRA (Hubbard et al., 1987). High concentrations of uranium and thorium cause the high HRZ gamma-ray log readings (Figure 1.5). The HRZ Formation also contains matrix-supported pebbles and frosted quartz grains and has been included in the pebble shale unit in the subsurface, a lithostratigraphic nomenclature that has been applied to rocks ranging in age from Late Jurassic to Late Cretaceous (Bird, 1985, Molenaar et al., 1987). Morgridge and Smith (1972) concluded that the HRZ was the main source of Prudhoe Bay area oils because it overlies the LCU truncation surface and is the only source rock directly in contact with each of the Ivishak, Lisburne, and Endicott reservoirs (Figure 1.4). From Early Cretaceous time until the present, the Brookian sequence was deposited in the Colville Trough in a northeastward-prograding wedge of sediment that was shed from the Brooks Range and the Herald Arch (Mull, 1985). Brookian sedimentation pushed Shublik, Kingak, and HRZ source rocks south and southeast of the fields into the oil window during Late Cretaceous to Paleogene time, when the focal point for oil migration was the Prudhoe/Kuparuk area of the Barrow Arch (Hubbard et al., 1987). The Tarn Field, which was discovered in 1997 and is currently producing 25,000 BOPD (4,000 cubic meters per day), is an oil accumulation in Upper Cretaceous deepwater Brookian sandstones in the southwestern part of the Kuparuk River Unit (Figure 1.1; Morris et al., 2000). The West Sak Field is a shallow, biodegraded Brookian oil accumulation in Upper Cretaceous shallow marine sandstones of the Schrader Bluff Formation informally known as the West Sak sands (Werner, 1987). An estimated 15 to 25 billion barrels (2.4 to 4 billion cubic meters) of oil in place are trapped in the West Sak sands over an area of 200 square miles (500 square kilometers) that mostly overlies the Kuparuk Field (Werner, 1987). Oil at the West Sak Field is trapped in several fault blocks bounded by north/northeast-striking faults that displace both the West Sak and underlying Kuparuk reservoirs (Figure 1.4). Except for a pilot waterflood test conducted from 1984 until 1986, no oil was produced from the West Sak Field prior to 1997 because of its relatively low oil gravity and high viscosity. In late 1997, development of the West Sak Field on the eastern side of the Kuparuk River Unit commenced with production of 1,000 BOPD (160 cubic meters per day) from three wells. The West Sak reservoir in this area produces oil ranging from 17 to 200 API gravity at a depth of 3,500 to 4,000 feet (1,000 to 1,200 meters) subsea. Chapter 2 presents evidence that West Sak oil is a mixture of moderately biodegraded oil that spilled from the Prudhoe Bay Field, and lightly biodegraded gas/condensate that leaked from the underlying Kuparuk Field. Between Paleogene time and the present, the reservoirs along the Barrow Arch were tilted 1-2 to the northeast (Wadman et al., 1979; Carman and Hardwick, 1983; Bird, 1985). This tilting event is hypothesized to have resulted from crustal loading caused by thrusting from 62 to 23 Ma

8 (Paleocene through Miocene) in the Arctic National Wildlife Refuge to the east (Masterson and Paris, 1987; OSullivan et al., 1993; Figure 1.1). Uplift and tilting created a north/northeaststriking fault system in the Kuparuk River field (Masterson and Paris, 1987). Carman and Hardwick (1983) hypothesized that Ivishak oil spilled into the Eileen fault system at the western end of the Prudhoe Bay Field and up into the Kuparuk reservoir in response to tilting. However, the composition of Kuparuk oil is not compatible with spillage from the Prudhoe Bay reservoir (Chapter 2). METHODS Geochemical data from 68 oils and 25 source rock extracts from the central Alaskan North Slope were used in the study (Figures 1.1, 1.6). Sample preparation and analytical techniques are described in Chapter 2. Additional description of gas chromatography-mass spectrometry-mass spectrometry (GC/MS/MS) and gas chromatography-isotope ratio mass spectrometry (GC/IRMS) methodologies are presented in Holba et al. (1998) and in Ellis and Fincannon (1998). Oil and rock samples were prepared at ARCO Exploration and Production Technology labs and at Baseline Resolution Inc. in Plano, TX. Whole oil gas chromatography and gas chromatography-mass spectrometry (GC/MS) analyses were performed at Baseline Resolution Inc. Carbon and sulfur stable isotope analyses were conducted by Coastal Science Laboratories in Austin, TX. Analyses of trace metals in oils were performed by Huffman Laboratories, Inc. in Golden, CO. Rock Eval analyses were provided by Humble Instruments and Services, Inc. in Humble, TX and by DGSI in The Woodlands, TX. Gas chemical and isotopic compositions were measured by Global Geochemistry in Los Angeles, California, and by ISOTECH Laboratories in Champaign, Illinois. GEOCHEMICAL EVALUATION OF POTENTIAL SOURCE ROCKS SHUBLIK FORMATION The Late Triassic Shublik Formation carbonates, marls, and phosphorites are the richest and volumetrically most significant source rocks in the central North Slope subsurface. There are many complete cores of the Shublik Formation because it was deposited between the Sag and Ivishak sandstone reservoirs. The organically richest facies of the Shublik Formation was deposited as black limestone, marl, and mudstone in a distal upwelling zone environment on a marine shelf (Parrish, 1987). Shublik source rocks in the Prudhoe Bay area were deposited within the transition zone between organic-rich facies to the southwest and phosphatic or glauconitic facies to the north (Kupecz, 1995). The siliciclastic component of Shublik facies increases towards its northern paleoshoreline, and in the northeastern part of Prudhoe Bay Field the Shublik interval consists mainly of shale and siltstone (Kupecz, 1995). The distal, organicrich facies of the Shublik Formation will be referred to as the calcareous facies in this study, and the more shoreward, proximal facies at Prudhoe Bay Field will be referred to as the shaly facies. The calcareous Shublik facies in the Phoenix #1 well north of the Colville Delta is an excellent source rock with 4% average total organic carbon (TOC), 24 mg/g S2, and hydrogen index values (HI = S2 x 100/TOC) up to 965 (Robison et al., 1996; Figure 1.7, Table 1.1). The S2 measurement is defined as the weight of hydrocarbons per gram of rock generated during heating in a Rock Eval instrument, and measures the potential to generate hydrocarbons during thermal

9 maturation (Espitali et al., 1977; Peters and Cassa, 1994). Source rocks with greater than 5 mg/g S2 and 300 HI are considered to have excellent potential to generate oil (Merrill, 1991). Shublik zone C has more potential to generate hydrocarbons than the overlying zone A in Phoenix #1, which Robison et al. (1996) attribute to a transgressive environment during deposition of zone C and a regressive environment during deposition of zone A. Shublik source rock contains both oil-prone, Type I and II kerogen, and gas-prone Type III kerogen (Figure 1.7). The identification of Type I kerogen is based solely upon hydrogen indices greater than 600 in some Shublik samples and does not imply a lacustrine environment of deposition for the Shublik Formation. Type I lacustrine source rocks often have a large proportion of algal organic matter (Peters and Cassa, 1994), and marine algal organic matter is also abundant in the Shublik Formation. Kerogen in the Shublik calcareous facies at the Phoenix #1 well is primarily fluorescent amorphous algal organic matter (amorphite), alginite, and exinite (spores, pollen, cutinite, and resinite), with lesser amounts of non-fluorescent amorphite, vitrinite, and inertinite (Robison et al., 1996). Shublik zone C in the Phoenix #1 well contains Type I and Type II kerogen that is relatively sulfur-rich, averaging > 2% sulfur, but zone A contains more Type III kerogen with < 2% average sulfur content (Robison et al., 1996). Shaly Shublik facies from Prudhoe Bay area wells fall more in the Type II and Type III kerogen categories based upon their hydrogen indices and have less organic carbon and sulfur than the Phoenix #1 calcareous facies (Table 1.1). All Shublik source rock extracts contain relatively high concentrations of tricyclic terpanes (Figure 1.8; Seifert et al., 1980). Aquino Neto (1992) suggested that tricyclic terpanes may be derived from tasmanites, a unicellular fossil microorganism that is found in Triassic rocks from northern Alaska and thought to be either green algae or green algal spores. Algal organic matter is common in Shublik source rock, but tasmanites has only been reported from Triassic rocks that crop out in the Brooks Range. Calcareous Shublik facies extracts also can exhibit relatively high ratios of dibenzothiophene (DBT)/phenanthrene and C29/C30 hopane, consistent with a sulfur-rich carbonate source rock (Figures 1.8, 1.9; Peters and Moldowan, 1993; Hughes et al., 1995). Shaly Shublik facies have higher pristane/phytane and Ts/Tm ratios and lower DBT/phenanthrene, C29/C30 hopane, C23 tricyclic terpane/C30 hopane, and C35/C34 homohopane ratios than calcareous Shublik facies, consistent with a more oxygenated environment and higher siliciclastic input to the shaly facies (Table 1.2). The average carbon isotopic compositions of saturated and aromatic hydrocarbon extracts from Shublik calcareous and shaly facies are similar, although the shaly facies exhibit more variability and fall more on the non-marine side of Sofers line (Figure 1.10; Sofer, 1984). The Shublik and Kingak core extract isotopic compositions shown on Figure 1.10 are significantly lighter (i. e., more negative) than the NPRA cuttings and core samples previously reported by Magoon and Bird (1985) and Claypool and Magoon (1985). In the case of cuttings samples, part of the discrepancy may arise from contamination by cavings from overlying isotopically heavy HRZ source rock that is not isolated behind casing in some NPRA wells. Part of the discrepancy also probably arises from the kinetic isotope effect produced by increased maturation of Shublik source rock in some parts of NPRA. Because 12C - 12C bonds require less energy to break than 12C - 13C bonds, maturation of kerogen should preferentially concentrate the 13C isotope, causing a kinetic isotope shift to heavier isotopic compositions in the kerogen (Stahl, 1977). For

10 example, the Shublik core from the Inigok #1 well in the NPRA (Figure 1.1) has an average Ro of 2.0% and Tmax of 5250C, and its saturate and aromatic fraction extracts are about 3 heavier than the extracts from the less mature Shublik cores in this study area (Claypool and Magoon, 1985). All of the Shublik shaly facies cores are located in the Prudhoe Bay Field, so some of the scatter in their isotopic compositions could be caused by contamination from the underlying Ivishak oil column. Possible contamination by migrated hydrocarbons can be assessed with the Rock Eval S1 measurement, which is a thermal extract of free and absorbed hydrocarbons (Espitali et al., 1977; Peters and Cassa, 1994). Magoon and Claypool (1984) interpreted S1/TOC values greater than 1 as an indicator of migrated hydrocarbons. Most of the S1/TOC values from source rock cores used in this study are less than 1 (Table 1.1). Shublik, HRZ, and Kingak core extracts from Prudhoe Bay Field are geochemically distinct from one another and from Prudhoe Bay crude oil (Figure 1.9), so significant contamination of the cores by Prudhoe Bay crude is unlikely. Many of the biomarker ratios for Shublik cores in the field are intermediate between calcareous Shublik facies and Kingak source rocks (Figure 1.9). From a geological standpoint, it is reasonable that shaly Shublik proximal source rock facies at Prudhoe Bay Field exhibit geochemical properties intermediate between calcareous Shublik facies and Kingak Shale siliciclastic source rock facies. The Kingak Shale is separated from the Shublik Formation by less than 50 feet (15 meters) of intervening Sag River Sandstone at Prudhoe Bay Field. KINGAK SHALE Kingak Shale kerogen is a mixture of marine and terrestrial organic matter deposited in a siliciclastic environment with no significant carbonate input (Magoon and Claypool, 1984). Although Kingak source quality is variable in the three cored wells (Table 1.1), the richest source interval is typically found near the base, directly overlying the Sag River Sandstone (Figure 1.5). The lowermost 50 feet (15 meters) of Kingak Shale in the Kalubik #1 well averages 5% TOC and 20 mg/g S2 in cuttings (Figure 1.5). Kingak kerogen in the cored wells falls in the Type II and Type III fields and is mostly amorphous or massive, with subsidiary alginite, inertinite, and vitrinite (Figure 1.7; Magoon and Claypool, 1984; J. R. Castao, written comm. 1996). Kingak core extracts are geochemically distinct from Shublik extracts and are easily distinguished with several biomarker parameters (Figure 1.9). Relative to Shublik extracts, Kingak extracts exhibit higher ratios of pristane/phytane and lower ratios of DBT/phenanthrene, C29/C30 hopane, C23 tricyclic terpane/C30 hopane, and C35/C34 homohopane. These geochemical differences are consistent with a more proximal, siliciclastic-dominated depositional environment and a higher proportion of non-marine organic matter in Kingak Shale kerogen. The carbon isotopic compositions of Kingak core extracts are quite variable and partially overlap the Shublik isotopic compositions (Figure 1.10). The isotopically heaviest (i. e., least negative) Kingak core extract is from PBU U-13 (Term Well B) in the Prudhoe Bay Field (Table 1.2). The U-13 Kingak core sample is located only two feet (0.6 meter) above an oil-saturated Sag River Sandstone and may be contaminated with Prudhoe Bay crude oil, although its S1/TOC value of

11 0.2 provides no evidence for contamination (Table 1.1). The Oliktok Point #1 Kingak core also overlaps Shublik isotopic compositions but is located in the Kuparuk River Field area more than 150 feet (45 meters) above a water-wet Sag River Sandstone and is therefore not likely to be contaminated with migrated oil. The remaining Kingak core extracts are all isotopically lighter than the Shublik core extracts, and there is a trend towards more non-marine isotopic composition with decreasing 13C concentration (Figure 1.10). Sedivy et al. (1987) noted that oilprone Kingak kerogen produces an isotopically lighter pyrolyzate than gas-prone Kingak kerogen. HRZ FORMATION The Lower Cretaceous HRZ Formation was deposited in a deepwater basin plain environment. Hydrogen indices of HRZ cores suggest a mix of Type II and Type III organic matter, consistent with a deepwater marine shale depositional setting outboard of the Nanushuk deltaic system (Mull, 1985; Figure 1.7). Petrographic observations indicate predominantly amorphous or massive kerogen along with alginite, vitrinite, and inertinite (Burkley and Castao, 1985). There are numerous HRZ cores in the study area, and all show good source rock quality with 2% to 7% TOC and hydrogen indices ranging from 150 to greater than 400 mg/g (Table 1.1). Most cores are from the base of the HRZ Formation and resulted from attempts to core the underlying Kuparuk reservoir or Ivishak reservoir beneath the LCU. Cuttings samples indicate good HRZ source rock quality throughout the zone of high gamma ray log readings (Figure 1.5). Some of the richest HRZ cores samples are located south of the Prudhoe Bay Field at the Hemi Springs #3 well and possess hydrogen indices approaching those of Type I kerogen (Table 1.1; Figure 1.7). Several biomarker ratios in HRZ source rock are similar to the Kingak Shale because both are marine shales with relatively high pristane/phytane ratios and low ratios of DBT/phenanthrene, C29/C30 hopane, C23 tricyclic terpane/C30 hopane, and C35/C34 homohopane relative to Shublik source rock (Figure 1.9). The C35/C34 homohopane ratio in HRZ extracts is similar to the Kingak average except for one HRZ sample from the Delta State #1 well that has a high C35 homohopane concentration. The most age-diagnostic biomarkers in HRZ extracts are C26 steranes (24-norcholestane and 24nordiacholestane) which are abundant only in Cretaceous and younger rocks (Holba et al., 1998). The 24-norcholestane biomarker is thought to originate from diatoms, which radiated in Cretaceous time and would have been abundant at the high paleolatitude of HRZ source rock deposition (Holba et al., 1998). The NDR ratio of 24-nordiacholestane to 24- and 27nordiacholestane averages 0.4 in HRZ extracts and less than 0.2 in Shublik and Kingak extracts (Table 1.2; Figures 1.9, 1.11). North Slope oils with NDR values less than 0.2 probably do not have any significant co-source from HRZ source rock. The percentage of C28 sterane is also unique in HRZ extracts, averaging 30% in comparison with Kingak and Shublik averages of 24 to 25% (Figure 1.9). The higher proportion of C28 steranes in HRZ kerogen may reflect a more diverse, geologically younger assemblage of

12 phytoplankton in Cretaceous time compared to Jurassic and Triassic time (Grantham and Wakefield, 1988). The carbon isotopic composition of HRZ core extracts is distinct from Shublik and Kingak core extracts. HRZ extracts are enriched in 13C by at least 0.7 in the aromatic fraction and do not overlap the Shublik and Kingak isotopic ranges (Figure 1.10). Most of the HRZ extracts fall on the non-marine side of Sofers line, likely reflecting input of terrestrial kerogen from the Nanushuk deltaic system. OTHER POTENTIAL SOURCE ROCKS Several other stratigraphic intervals in the North Slope subsurface ranging in age from Mississippian to Tertiary have sufficient organic carbon content to be considered potential source rocks (Morgridge and Smith, 1972; Seifert et al., 1980; Magoon and Bird, 1985; Sedivy et al., 1987; Holba et al., 2000). Geochemical evidence presented in this chapter suggests that Lisburne Group carbonates are a source of both oil and gas in the study area. Sedivy et al. (1987) report an average value of 0.7% TOC for carbonates of the Lisburne Group. Although 0.7% would be considered too lean for a good siliciclastic source, it exceeds the 0.6% average TOC reported for carbonate source rocks by Tissot and Welte (1984). Lisburne Group shales with up to 14% TOC have been encountered in the Prudhoe Bay Field area, and it is likely that Lisburne source quality increases to the south in the Colville Trough oil kitchen in a more distal carbonate ramp depositional setting. Brosg et al. (1981) report organic carbon contents of up to 7% for highly mature (Ro > 3%) Lisburne carbonates exposed in the Brooks Range south of the Colville Trough. In addition to the HRZ Formation, there are potential Cretaceous source rocks in the Torok Formation and other intervals in the Colville Group (Sedivy et al., 1987; Magoon and Bird, 1985). It is possible that these other Cretaceous source rocks will generate isotopically heavy oils with high values of NDR and thus may be confused with HRZ-sourced oils. The other potential Cretaceous sources were not examined in this study because few cores are available, and it must be acknowledged that they are a potential co-source for oils that are attributed to a HRZ source. However, the HRZ Formation is the richest source rock in the Cretaceous section (Sedivy et al., 1987) and likely generated the majority of the Cretaceous-sourced oil in the study area. ORIGIN OF OILS KUPARUK AND ALPINE FIELDS Kuparuk Field oils are remarkably uniform in composition and are interpreted as sourced from the Shublik Formation, with a possible minor contribution from the Kingak Shale in the southwestern part of the field. The average API gravity of 230, sulfur content of 1.6%, and asphaltene concentration of 19% in Kuparuk Field oils (Table 1.3) are consistent with derivation from the Shublik Formation or another carbonate-rich source interval rather than from a shale. The carbon isotopic compositions of saturated and aromatic fractions from the field fall into the range of overlap between extracts from calcareous and shaly Shublik source rock facies (Figures 1.10, 1.12). Biomarker ratios in Kuparuk Field oils are all similar to calcareous Shublik source rock extracts, with the exception of the pristane/phytane ratio that is intermediate between shaly and calcareous Shublik facies. The Kuparuk Field is located between predominantly calcareous

13 Shublik facies penetrated by the Phoenix #1 well and the predominantly shaly Shublik facies at Prudhoe Bay Field, so it is reasonable that Kuparuk oil isotopic composition and some biomarker ratios would be intermediate between the two facies of the Shublik Formation. An important point of control for the maturity of the underlying Shublik source rock in the Kuparuk Field area is provided by a core and an oil tested from the Shublik interval in the Colville #1 well located 5 miles (8 km) west of the field (Figure 1.6). There can be little doubt about the source of the Colville #1 oil, because it was tested from the Shublik interval in the well, and the underlying Ivishak sandstone reservoir produced only water when tested. A core of the Shublik interval in the well yielded vitrinite reflectance values ranging from 0.93 to 1.14% Ro, placing it in the middle to late oil window. A late oil window maturity is suggested by the Colville #1 well test that flowed gas with a little oil at a rate of 5 to 8 million cubic feet per day from the Shublik interval, and is also indicated by the thermal destruction of hopanes in the oil and the relatively high ratio of Ts/Tm (Table 1.3, Figure 1.8). The Ts/Tm ratio of 7.6 in Colville #1 oil is much higher than the ratios observed in immature Shublik source rock facies (Table 1.2), and the Ts/Tm ratio is primarily an indicator of maturity in oils (Peters and Moldowan, 1993). The relatively heavy carbon isotopic composition of the Colville #1 oil relative to the Kuparuk Field oils is consistent with a kinetic isotope shift of about 0.5 due to increased Shublik source rock maturity (Figure 1.12). The relatively high gravity (360 API) and low sulfur content (0.66%) of the Sinclair Colville #1 Shublik oil can therefore be attributed to increased maturation of the Shublik source rock. The increase in Shublik source rock maturity from 0.7% Ro at the eastern side of the Kuparuk Field to 1% Ro at the Colville #1 well is not reflected in the biomarker maturity ratios in Kuparuk Field oils, possibly because the biomarker ratios are heavily weighted towards the high concentrations of biomarkers in oils generated at early oil window maturities. For example, the concentrations of Ts and Tm in relatively immature Phoenix #1 Shublik core extracts average 500 ppm and are an order of magnitude higher than the average 50 ppm concentrations in the more mature Shublik core from the Colville #1 well (Table 1.4). The Ts/Tm ratio in oil tested from the Shublik interval in the Colville #1 well is much higher than in Kuparuk Field oils (Table 1.3), but addition of the low concentrations of Ts and Tm that are present in late-maturity Shublik-sourced oil would have little effect upon the higher Ts and Tm concentrations in Kuparuk Field oils that were generated in the early oil window. The only other North Slope source interval that could conceivably source the high-sulfur, asphaltene-rich oils of the Kuparuk Field is the Carboniferous Lisburne Group. The Lisburne Group is interpreted as the source of an oil tested from Lisburne carbonates at the 2F-20 well in the Kuparuk Field (McCaffrey and Holba, written comm. 1998; Figure 1.6). The 2F-20 Lisburne oil exhibits extremely high ratios of DBT/phenanthrene, C29/C30 hopane, C23 tricyclic terpane/C30 hopane, and Ts/Tm. The MPI-1 calculated maturity of 0.9% Ro equivalent for the Lisburne 2F-20 oil is the highest for any oil in Table 1.3. The relatively high API gravity of 330 and low sulfur (0.7%) and asphaltene (1%) contents in 2F-20 oil suggest that it was generated at high maturities similar to that of the Shublik oil tested from the Colville #1 well, and do not necessarily preclude the Lisburne Group as a source for Kuparuk Field oils at lower Lisburne thermal maturity. However, the dinosterane ratio of < 0.01 differs markedly from Kuparuk Field oils and indicates that the 2F-20 oil was sourced from a Paleozoic source rock that pre-dates the

14 Triassic radiation of dinoflagellates (Moldowan et al., 1996), consistent with a Lisburne Group source. All of the other North Slope oils that were sourced by Triassic and younger intervals have dinosterane ratios of at least 0.2. Because Kuparuk Field oils have a dinosterane ratio close to the average for distal Shublik source rock, they probably were not diluted by any volumetrically significant contribution from Lisburne-sourced oil, although the dinosterane ratio in 2F-20 oil may have been affected by the high maturity of the oil. In addition, the 24% average C28-sterane concentration in Kuparuk Field oils closely matches the average for Shublik source rock but differs from the 32% value in the Lisburne 2F-20 oil. Nevertheless, a small Lisburne Group co-source to Kuparuk Field oils cannot be completely ruled out, and could explain why the C29/C30 hopane ratios in Kuparuk Field oils are slightly higher than the average C29/C30 hopane ratio in Shublik calcareous source rocks (Table 1.3). The Kingak Shale is interpreted as the source of the high-gravity, low-sulfur oil at the Alpine Field. Evidence for mixing of Shublik and Kingak-sourced oils in the Kuparuk and Alpine Field area is provided by bulk properties, biomarker ratios, sulfur isotopic compositions and trace metal contents in the Kavearak Point, Alpine Field, and Fiord #1 Kuparuk oils (Figure 1.8). The Kavearak Point oil was tested from a reservoir reported to be of Jurassic age and interpreted as sourced solely from the Kingak Shale (Seifert et al., 1980; Premuzac et al., 1986). The Kavearak Point and Alpine Field oils are interpreted to have been sourced from the Kingak Shale because of their low sulfur content (< 0.3%), high API gravity (36 to 39), low nickel and vanadium concentrations (< 5 ppm), light carbon isotope ratios (13Csat < -30.7 and 13Caro < -30), light sulfur isotopic composition (< -5CDT), low DBT/ phenanthrene ratio (< 0.56), low concentration of C29 hopane (C29/C30 hopane < 0.5), and low concentrations of tricyclic terpanes (C23 tricyclic terpane/C30 hopane < 0.2) that are similar to Kingak source rock extracts (Figures 1.8, 1.13). In contrast, Kuparuk Field area oils that are interpreted as sourced from the Shublik Formation have higher sulfur content (> 0.6%), moderate API gravities (< 27, with the exception of the high-maturity Sinclair Colville #1 oil discussed previously), higher nickel and vanadium concentrations (> 15 ppm), heavier carbon isotope ratios (13Csat > -30.2 and 13Caro > -29.8), heavier sulfur isotope ratios (> -1CDT), high DBT/phenanthrene ratios (> 0.56), higher concentrations of C29 hopane (C29/C30 hopane > 0.8), and higher concentrations of tricyclic terpanes (C23 tricyclic terpane/C30 hopane > 0.3). Oils with intermediate compositions, for example the oil tested from the Kuparuk reservoir in the Fiord #1 well (Figure 1.8), are interpreted as mixtures that were co-sourced by both Shublik and Kingak source rocks. Biomarker parameters sensitive to Kingak and Shublik co-source proportions such as the C29/C30 hopane ratio are highly correlated with the API gravity of the produced oil (Figure 1.14). This correlation can be used in old cores or cuttings to predict the API gravity of oils from zones that were not tested; for example, an oil gravity of 290 API is predicted for the Jurassic reservoir that was cored but not tested in the Nechelik #1 well. This API gravity prediction is valid only for early to middle oil window maturities and cannot be used to predict the gravity of oils like the Sinclair Colville #1 Shublik-sourced oil that were generated in the late oil window. Some oils in the southwestern part of the Kuparuk Field at Central Production Facility 2 (i. e. 2A-2 and 2B-5 oils; Table 1.3) have lower C29/C30 hopane and C23 tricyclic terpane/C30 hopane ratios than the field average and may have a slight (~10%) co-source from the Kingak Shale. The C23 tricyclic terpane/C30 hopane ratio would be expected to increase towards the west with increasing maturity of the underlying Shublik source rock, as evidenced by the

15 extremely high ratio in the Colville #1 Shublik oil (Figure 1.8). The observed decrease of these ratios in the southwestern part of the Kuparuk Field suggests dilution by Kingak-sourced oil. A mixture of 10% Kingak-sourced oil and 90% Shublik-sourced oil could account for the lowered C23 tricyclic terpane/C30 hopane and C29/C30 hopane ratios in the southwestern part of the Kuparuk field. However, the carbon isotopic composition of Kuparuk oils does not decrease towards the southwest as expected if it mixed with an isotopically lighter Kingak-sourced oil, and the biomarker ratios in Kuparuk oils all fall within the range of Shublik source rock facies, so evidence for a Kingak co-source is equivocal. It is possible that isotopically light oil sourced from the Kingak Shale in the southwest part of the field is masked by increased maturity, and heavier isotopic composition, of the dominant Shublik co-source. Dilution by HRZ-sourced oil would have the same effect on the C29/C30 hopane and C23 tricyclic terpane/C30 hopane ratios but can be ruled out in the case of Kuparuk Field oils because there is no other biomarker or isotopic evidence for an HRZ co-source. In addition, the HRZ Formation is immature in the Kuparuk Field area (Chapter 3) and is separated from the underlying Kuparuk reservoir by about 100 feet (30 meters) of Kalubik Formation mudstone (Figure 1.4). TARN FIELD AND OTHER OILS SOURCED FROM CRETACEOUS ROCKS The HRZ Formation is interpreted as the source of oil at the Tarn Field in the extreme southwestern part of the Kuparuk River Unit (McCaffrey and Holba, written comm. 1997; Figure 1.1). The Tarn Field produces 380 API gravity oil from the Upper Cretaceous Bermuda Sandstone. Upper Cretaceous rocks at Tarn Field downlap on the HRZ source interval to the east of the field (Figure 1.3). The high gravity, low sulfur (0.2%), low asphaltene content (2%), relatively heavy carbon isotopic composition, low DBT/phenanthrene ratio, low tricyclic terpane concentration, high percentage of C28 steranes, and high NDR ratio are indicative of an HRZ source for the Tarn oils (Figures 1.12, 1.15). Biomarker ratios in the Umiat #4 oil (Figure 1.1) are similar but not identical to Tarn oils and to HRZ source rock (Figure 1.15, Table 1.3). The NDR value of 0.44 in Umiat #4 oil indicates a Cretaceous or younger source. Magoon and Bird (1985) suggested that the Torok Formation might be the source of Umiat Field oils. The Torok Formation is the Lower Cretaceous deep marine offshore equivalent of the prograding deltaic Nanushuk Group and downlaps on HRZ basin plain deposits (Bird, 1985). Umiat #4 oil is isotopically heavier than Tarn oil and falls outside the isotopic range of the HRZ source rock core samples in this study (Figure 1.12). The heavier carbon isotopic composition of Umiat #4 oil could be caused by higher maturity of source rock in the Colville Trough at the Umiat Field 50 miles (80 km) south of Tarn Field, or could be due to the heavier isotopic composition of Torok-sourced oil relative to HRZ-sourced oil. Biomarker maturity ratios provide no evidence for higher maturity of Umiat #4 oil relative to Tarn #2 oil, and the differing values of pristane/phytane, C35/C34 hopane, %C28 steranes, Ts/Tm, and dinosterane suggest that either a Torok source or source facies variations in the HRZ Formation could account for the differences between Umiat and Tarn oils. The HRZ Formation is interpreted as the source of the oil tested from shallow Upper Cretaceous sandstones in the Kuukpik #3 well northwest of the Kuparuk Field (Figures 1.6, 1.12). Biodegradation has removed the n-alkanes from Kuukpik #3 oil, which accounts for its lowered API gravity (220), slightly elevated sulfur content (0.4%), higher C29 25-norhopane/C30 hopane

16 ratio, and heavier carbon isotopic composition of its saturated hydrocarbons relative to Tarn oil (Table 1.3, Figure 1.12). The NDR ratio of 0.55 in the Kuukpik #3 oil indicates a Cretaceous or younger source. PRUDHOE BAY MAIN FIELD The oils in the Ivishak reservoir of the Prudhoe Bay main field area (east of the SE Eileen St. #2 well; Figure 1.6) are interpreted to have been sourced mainly from the Shublik Formation, with lesser contributions from the HRZ Formation and the Kingak Shale. The average 290 API gravity of Prudhoe main field oils is higher than the 230 API average of Kuparuk Field oils, and the sulfur and asphaltene content of Prudhoe crude is less than Kuparuk Field crude (Figure 1.16; Table 1.3). These bulk property differences between Kuparuk Field and Prudhoe Bay Field oils are caused by dilution of Shublik-sourced oil by HRZ and Kingak-sourced oils at Prudhoe. The average 1% sulfur in Prudhoe Bay main field oils, 1.6% sulfur in Kuparuk Field oils, and 0.2% sulfur in Kingak and HRZ-sourced oils suggests that about 60% of the Prudhoe Bay main field oil was sourced from the Shublik Formation. Biomarker ratios in Prudhoe main field oils are generally intermediate between Shublik, Kingak, and HRZ source rocks, with the exceptions of DBT/phenanthrene, which matches the calcareous Shublik source rock average, and the %C28 sterane and NDR values, which match the HRZ source rock averages (Figure 1.9). The carbon isotopic compositions of Prudhoe main field oils are intermediate between Shublik and HRZ source rock extracts, providing further evidence for Shublik and HRZ co-sources (Figure 1.12). The NDR ratio provides compelling evidence for HRZ contribution to Prudhoe main field oils because C26-sterane 24-norcholestanes are found in significant quantities in HRZ source rock but are present only in trace amounts in Kingak and Shublik source rocks (Figure 1.11; Holba et al., 1998). It is interesting to note that even though the HRZ is a rich source rock in direct contact with the Ivishak reservoir and had been suggested as a source of Prudhoe Bay oil by several authors (Morgridge and Smith, 1972; Seifert et al., 1980), only 1 out of 26 geochemical laboratories identified the HRZ Formation as a co-source of Prudhoe Bay Field oil in the 1983 Alaska North Slope oil-rock correlation study (Claypool and Magoon, 1985). Most of the laboratories identified the Shublik Formation and, to a lesser extent, the Kingak Shale as the sources for Prudhoe Bay oil. Evidence for a Kingak co-source to Prudhoe main field oil is not as compelling as evidence for HRZ co-source, but can be inferred from carbon isotopic and biomarker compositions of oils and core extracts. Evidence for a Kingak co-source is shown on Figure 1.17, where the isotopic composition of the C15+ aromatic fraction of Prudhoe main field oils is lighter than predicted by mixing solely between Shublik-sourced Kuparuk Field oils and HRZ-sourced oils. Kingaksourced oil similar in isotopic composition to the Kavearak Point oil would be required to provide the isotopically light co-source that shifts Prudhoe oils off of the Shublik/HRZ twocomponent mixing line. The isotopic composition of the Kavearak Point oil is outside the range of Kingak core extracts (Figure 1.12) and possibly was generated from a northerly, more proximal Kingak Shale facies that has not been recovered in core to date. The Ivishak reservoir in the Prudhoe Bay main field gas cap has a residual oil saturation of up to 10% that pre-dated the migration of gas into the field. Core extracts from the Prudhoe Bay main field gas cap have isotopic compositions similar to Shublik source rock extracts (Figure 1.18),

17 but also exhibit relatively high NDR ratios indicative of a substantial co-source from the HRZ Formation (Figure 1.17). Because the HRZ co-source is isotopically heavier than Shubliksourced oil (Figure 1.10), a Kingak-sourced oil or another isotopically light oil must have mixed with the Shublik and HRZ co-sources in order to produce an oil with an isotopic composition near the average for Shublik source rock. The relatively high NDR ratio in the Prudhoe Bay Main Field gas cap core extracts suggests that an HRZ charge reached the crest of the Prudhoe Bay paleo-structure prior to formation of the main gas cap (Figure 1.18). If the HRZ oil charge arrived at the Prudhoe Bay Field after formation of the gas cap, it is difficult to imagine how it could have drained into the gas cap from above through the small, presumably non-continuous residual oil phase trapped in the gas cap. Extracts from core in the light oil column of Prudhoe Bay Field fall mostly between Shublik and HRZ extracts and exhibit the same general isotopic compositions as Prudhoe main field oils (Figures 1.12, 1.18). The biomarker and isotopic composition of the residual oil in the Prudhoe Bay main field gas cap suggests that a mixed Shublik/HRZ/Kingak oil charge was present in the Prudhoe paleo-trap before gas began to migrate into the structure. The present-day Prudhoe Bay light oil and tar mat is isotopically heavier than the residual oil in the gas cap (Figures 1.12, 1.18), which suggests a higher proportion of HRZ co-source to the oil charge that reached the Prudhoe structure after formation of the gas cap. A few extracts from the light oil column exhibit relatively heavy isotopic compositions similar to HRZ core extracts, providing further evidence for an HRZ co-source to Prudhoe oils (Figure 1.18). The oil tested from the Kuparuk reservoir in the N Kuparuk 26-12-12 well falls near the Shublik/HRZ mixing line and is interpreted to have been co-sourced by the Shublik and HRZ Formations with little or no co-source from the Kingak Shale (Figure 1.17). The Kuparuk reservoirs near the west end of the Prudhoe Bay Field are in direct contact with the HRZ Formation because the intervening Kalubik Formation shale is absent in part of the area (Figure 1.4). The absence of the Kalubik Formation allowed HRZ oil charge to reach the Kuparuk reservoirs in this area. PRUDHOE BAY MAIN FIELD TAR MAT The Prudhoe Bay main field Ivishak accumulation has a basal tar mat that extends 20 to 60 feet (6 to 18 m) up from the oil-water contact at about 9020 feet subsea (Wadman et al., 1979; Figure 1.6). The tar mat is present everywhere along the southern and western downdip limits of the main field but does not extend west of the SE Eileen #2 well into the West End accumulation except for isolated, patchy occurrences. The tar mat is enriched in asphaltenes relative to main field light oils but is not biodegraded and is otherwise geochemically similar to the overlying light oil column. The carbon isotopic compositions of core extracts from the heavy oil and tar mat zones are similar to Prudhoe main field oils (Figures 1.12, 1.18). Rodgers et al. (1974) reported that the carbon isotopic compositions of bitumens formed by gas deasphalting are similar to the compositions of the unaltered oil, as observed at the Prudhoe Bay Field tar mat. A zone of residual oil staining beneath the present-day field oil-water contact (OWC) also has a similar isotopic composition to Prudhoe Bay crude oil (Figure 1.18). The presence of residual oil beneath the present-day main field OWC indicates that the Prudhoe Bay field oil-water contact was deeper in the past.

18 Gravity segregation probably contributed to the formation of the Prudhoe Bay Field tar mat. Asphaltene-rich fluids are theoretically predicted to segregate at the base of oil columns in response to the force of gravity (Schulte, 1980). The API gravity of the light oil column systematically increases from less than 200 at the top of the tar mat up to 300 at the gas oil contact, consistent with gravity segregation (Figure 1.18). The absence of a thick tar mat at the Lisburne pool carbonate reservoir, which shares approximately the same fluid contacts and filling history as the overlying Prudhoe Bay main field, suggests that a highly porous and permeable reservoir is also a requirement for tar mat formation. The oil-water contact in the Lisburne pool is not planar and apparently varies over a vertical depth range of 300 feet (100 meters) for reasons that are poorly understood, possibly related to permeability variations or Tertiary tectonic tilting (Missman and Jameson, 1991). The Ivishak Sandstone reservoir at Prudhoe averages 22% porosity and 265 millidarcies permeability, but the Lisburne reservoir averages only 10% porosity and <2 millidarcies permeability (Alaska Oil and Gas Conservation Commission, 1999). Gas stripping and deasphalting of the oil column probably also contributed to the formation of the Prudhoe tar mat. Tar is sometimes observed to be concentrated beneath shales at the top of sandstone beds in the tar mat. Tar formation beneath shales can result from gas migrating along the tops of permeable beds and deasphalting the oil column (Evans et al., 1971; Wilhelms and Larter, 1995). The Pt. McIntyre Kuparuk sandstone possesses excellent reservoir properties, and its hydrocarbon compositions and fluid contacts are almost identical with the Prudhoe Bay main field, yet there is no tar mat at Pt. McIntyre Field. The only major geochemical difference between the Pt. McIntyre and Prudhoe Bay main field accumulations is the lower concentration of CO2 in Pt. McIntyre oils and gases (Tables 1.3, 1.5). This observation suggests the possibility that the Prudhoe Bay tar mat formed in response to a CO2-rich gas charge that is absent at the Pt. McIntyre Field. It is unclear, however, whether the presence of CO2 in the gas charge is a critical requirement for formation of the tar mat at Prudhoe Bay. Since CO2-rich gas has not been reported as a necessary component for formation of tar mats elsewhere in the world, it seems likely that the gas charge is the critical factor, irrespective of the CO2 concentration in the gas. An entry point for the gas at the Prudhoe oil-water contact may be equally important because gravity segregation will tend to concentrate asphaltenes at the base of the oil column where a gas charge can migrate into the accumulation from the underlying aquifer (Figure 1.19). A bottomhole water sample from the Ivishak sandstone aquifer in a Prudhoe Bay Field development well contained 22.3 standard cubic feet of dissolved gas per stock tank barrel of water with a 31% CO2 concentration. At Pt. McIntyre Field, the maximum concentration and presumed entry point for CO2-rich gas is near the southern bounding fault for the field rather than at the oil-water contact (Figure 1.20), which may account for the lack of a tar mat at Pt. McIntyre. PRUDHOE BAY FIELD WEST END Oils produced from the Ivishak Formation in the West End of Prudhoe Bay Field are compositionally distinct and are interpreted to have less HRZ co-source than the main field Ivishak oils. West End Ivishak oils have slightly lower API gravity than main field oils, about the

19 same sulfur content, and higher asphaltene content (average 18% versus 7% average asphaltenes in main field oils; Table 1.3). Some of the difference in asphaltene content between the West End and main field oils may be attributable to the fact that the West End wells in Table 1.3 were all sampled within 110 feet (35 meters) of the oil-water contact, and their asphaltene content may be enhanced by gravity segregation. However, the lower percentage of C28 steranes and lower NDR ratio of West End Ivishak oils relative to the main field provide additional evidence for less HRZ input into the West End Ivishak oil. The carbon isotopic composition of West End Ivishak oils is also lighter than main field oils, overlapping more with the Shublik and Kingak core extracts (Figures 1.12, 1.17), again consistent with less HRZ input. The unique composition of West End Ivishak oils and difference in fluid contacts casts doubt on Carman and Hardwicks (1983) suggestion that the West End oils spilled from the Prudhoe Bay main field. The West End accumulation gas-oil contact (GOC) is about 200 feet (60 meters) deeper than the main field GOC and its oil-water contact (OWC) is about 60 feet (20 meters) shallower than the OWC at the base of the main field tar mat (Wadman et al., 1979). If Prudhoe main field oil had simply spilled into the West End during Tertiary eastward tilting as suggested by Carman and Hardwick (1983), the oil-water contacts should be identical and the main field oil leg would have spilled westward into the West End without forming a gas cap. The geochemical differences between West End and main field oils indicate that if Prudhoe main field oil spilled into the West End, the spilled oil must have been augmented by a separate oil and gas charge that contained less HRZ co-source than main field oils. Two West End oils tested from the Sag River Sandstone are interpreted as mixtures sourced from the Kingak Shale and the Shublik Formation. The West End Sag oils average 360 API gravity, identical to the Kingak-sourced oil tested from the Kavearak Point well, and exhibit similar sulfur and asphaltene concentrations (Figure 1.8, Table 1.3). A correlation based strictly on API gravity, sulfur, and asphaltene concentrations would indicate a predominant Kingak source for the West End Sag oils, but some biomarker ratios in the oils are intermediate between Shublik and Kingak source rocks (i. e. C23 tricyclic terpane/C30 hopane and C35/C34 homohopane; Figure 1.13). Because the Sag sandstone reservoir is in direct contact with underlying Shublik source rock, it is possible that the biomarker signature of the Shublik co-source in the oil is enhanced with bitumen extracted from Shublik source rock, a process known as reservoir overprinting (Hughes and Dzou, 1995). In addition, because some biomarkers in Shublik core extracts are present in higher absolute concentrations than in Kingak core extracts, a mix of Shublik and Kingaksourced oil could produce biomarker ratios that are skewed towards Shublik source rock. For example, C23 tricyclic terpane, C34 homohopane, and C35 homohopane concentrations in calcareous Shublik core extracts are several times higher than concentrations in Kingak core extracts (Table 1.4), and any mix of calcareous Shublik and Kingak-sourced oil will likely be skewed towards the ratios observed in Shublik source rock extracts for these biomarkers. In contrast, compounds such as dibenzothiophene and phenanthrene are present in approximately equal absolute concentrations in Shublik and Kingak core extracts, and should more accurately reflect the true co-source proportions. This provides a potential explanation for why DBT/phenanthrene ratios in West End Sag oils are similar to Kingak source rock extracts, but ratios of C23 tricyclic terpane/C30 hopane and C35/C34 homohopane are intermediate between Shublik and Kingak source rock extracts (Figure 1.13).

20 Carbon isotope ratios in the West End Sag River Sandstone oils are intermediate between Shublik source rocks and Kavearak Point oil, and the low NDR ratio indicates a lack of HRZ source input to the West End Sag oils (Figure 1.17). Because the Sag River Sandstone reservoir is sandwiched between Kingak and Shublik source rocks, it is geologically reasonable that they are the co-sources for the oil. The lack of HRZ co-source implies that the Sag and Ivishak reservoirs are not in hydrocarbon communication in this part of the West End, because the underlying Ivishak oils have an HRZ co-source (compare the NDR values for the Ivishak and Sag oils from the W Kuparuk 3-11-11 well; Table 1.3). The Sag River Sandstone reservoir at the N Kuparuk 26-12-12 well also has little or no HRZ co-source (Figures 1.6, 1.17). POINT MCINTYRE FIELD Oils produced from the Kuparuk reservoir at the Point McIntyre Field are geochemically similar to Prudhoe Bay main field Ivishak oils and are interpreted to have been co-sourced from Shublik, HRZ, and Kingak source rocks in approximately the same proportions as the Prudhoe Bay main field oils (Table 1.3). The southern bounding fault for the Point McIntyre accumulation is only a mile north of the northern bounding fault for the Prudhoe Bay Field (Figure 1.20), and the gas-oil and oil-water contacts for the two fields are nearly identical. The filling histories of the Prudhoe Bay and Point McIntyre Fields therefore appear to have been similar, with the exception of a CO2-rich gas charge at Prudhoe that is not present at Point McIntyre Field except in its southeastern portion (Figure 1.20, Table 1.5). WEST SAK FIELD With the exception of alteration caused by biodegradation, West Sak Field oils are geochemically similar to Prudhoe Bay Field oils and differ substantially from the underlying Kuparuk Field oils. Carman and Hardwick (1983) suggested that West Sak Field oils spilled from the deeper Prudhoe Bay Field during Tertiary eastward tilting. The oil accumulations in West Sak reservoirs are observed to stairstep downdip to the east for about 10 miles (16 kilometers) until they reach the western area of the Prudhoe Bay Field (Figure 1.4). In order for Prudhoe and West Sak oils to have similar biomarker signatures (Figures 1.11, 1.21), they must have been generated from the same source rocks in approximately the same proportions. The only plausible scenario in which the biomarker signatures of West Sak oils could so closely resemble biomarkers in Prudhoe oil is by remobilization of a previously mixed Prudhoe oil that spilled from the Prudhoe trap and remigrated approximately 10 miles (16 kilometers) laterally and 5,000 feet (1,525 meters) vertically into the West Sak Field (Figure 1.4). The elevated sulfur concentration of West Sak oil relative to Prudhoe oil could be due to biodegradation and preferential removal of alkanes and aromatic compounds with a corresponding increase in the relative concentrations of sulfur-rich asphaltene and polar compounds. West Sak oils have been moderately to heavily biodegraded and have lost essentially all of their normal alkanes and isoprenoids heavier than n-C12 (dodecane), yet also contain anomalously high concentrations of gasoline-range saturate and aromatic compounds that are not expected at this level of biodegradation (Figure 1.21; Chapter 2). The least biodegraded West Sak Field oils are found in zone A at the base of the reservoir, and the level of biodegradation increases upwards in zones B and D (Chapter 2). West Sak oils exhibit relatively high concentrations of

21 C29 25-norhopane, a biomarker that is produced during biodegradation (Figure 1.21; Moldowan and McCaffrey, 1995). Chapter 2 presents geochemical evidence that after Prudhoe Bay Field oil spilled into the West Sak reservoir and was biodegraded, gas and condensate leaked from the underlying Kuparuk Field and was lightly biodegraded in the shallowest West Sak reservoirs. West Sak oil is therefore interpreted as a mixture of moderately biodegraded oil that spilled from Prudhoe, and lightly biodegraded gas and condensate that leaked from the underlying Kuparuk Field. The NDR ratios of West Sak zone A oils are very similar to Prudhoe Bay main field oils (Figure 1.11), suggesting that spillage of West Sak oil originated from the Prudhoe main field rather than from the West End. Both the NDR and dinosterane ratios in West Sak oils are slightly altered by biodegradation in the shallowest reservoirs (compare West Sak zones A and D on Table 1.3), but the increase in the NDR ratio caused by biodegradation is not large enough to affect the correlation with Prudhoe oils. For example, the 50% increase in the C29 25-norhopane/C30 hopane ratio between zones A and D in the WSP 8I well is accompanied by an increase of only 5% in the NDR ratio (Table 1.3). ORIGIN OF GASES INTERPRETED END-MEMBER GASES FROM A SINGLE SOURCE The sources of gases are more difficult to interpret than oil sources because the only geochemical tools available are gas compositions and stable isotopes, and the database is more limited because of failure to analyze and preserve samples of gases tested from early exploration wells. The geochemical evidence for mixing of North Slope oils discussed above suggests that mixed gases are likely to be a common occurrence in the study area. In order to interpret the origin of mixed gases, the first step is to try and identify end member gases that were generated from a single source rock. In theory, the carbon isotopic compositions of gases sourced from a single isotopically homogenous source rock should plot as an approximately straight line on a natural gas plot (Chung et al., 1988; Figure 1.22). The natural gas plot is constructed in such a way that the carbon isotopic values for methane, ethane, propane, and n-butane are plotted along a scale that is the inverse of the carbon number for each molecule, and extrapolation of the ? 13C values to infinite carbon numbers (1/Cn = 0) yields a rough estimate of the carbon isotopic composition of the kerogen in the source rock (Chung et al., 1988). Unfortunately, the only North Slope gases that exhibit an approximately linear relation between isotopic composition and inverse carbon number on Figure 1.22 are the West End Prudhoe gas that was tested from an unnamed well, the Kalubik #1 solution gas that was tested from the Kuparuk Formation in the well, and the gas tested from the Lisburne Group in the 2F-20 well. The isotopic compositions of ethane and propane in the Prudhoe West End gas are very similar to solution gas from the Shublik-sourced oil tested from the Kalubik #1 well (Figure 1.22). Biomarkers in the West End Ivishak oils also indicate a predominant Shublik source, so it is reasonable to interpret that both the West End Prudhoe gas and the Kalubik #1 solution gas are sourced predominantly from the Shublik Formation, although the identity of the West End gas well is not reported in Chung et al. (1988). Extrapolation of the West End and Kalubik gas isotopes to infinite carbon numbers implies a kerogen isotopic composition of about -30, similar to the isotopic composition of the saturate and aromatic fractions of Shublik source rock

22 extracts (Figure 1.10). Sedivy et al. (1987) reported a ? 13C value of -29.64 0.74 for the pyrolyzate generated from Shublik kerogen. Gas wetness and methane isotopic compositions in Kalubik #1 Kuparuk gas are consistent with an oil-associated gas (Figures 1.23, 1.24), although the calculated maturity of the Kalubik #1 gas is about 1.4% Ro equivalent using the method of James (1990; Figure 1.25). The gas that was tested from Lisburne carbonates in the KRU 2F-20 well is interpreted as an end member gas sourced from the Lisburne Group. A Lisburne source for the gas is consistent with the relatively high-maturity Lisburne-sourced oil that was tested from the well. The 2F-20 Lisburne gas has a concentration of 17% CO2 and is also quite dry (Table 1.5). Gas wetness and methane isotopic compositions in the 2F-20 gas indicate a condensate-associated gas with relatively high maturity, possibly derived from oil cracking (Figures 1.23, 1.24). A maturity of about 1.6% Ro is calculated for the 2F-20 gas using the method of James (1990; Figure 1.25). The carbon isotopic composition of carbon dioxide in 2F-20 gas is 0.8PBD, within the range of +0.6 ? 1.5 reported for marine carbonate rocks of Cambrian to Tertiary age by Keith and Weber (1964), suggesting an inorganic origin for the CO2. Diagenetic dolomite in the Wahoo Formation of the Lisburne Group at Prudhoe Bay Field has a carbon isotopic composition between +3 and +4PBD and is often associated with pore-filling kaolinite cement (Jameson, 1994). Muffler and White (1968) reported that at temperatures greater than 1500C, dolomite reacts with kaolinite to produce chlorite, calcite, and CO2 in the Salton Sea geothermal system. It is therefore possible that the CO2 in the 2F-20 Lisburne gas was derived from high-temperature (> 1500C) decarbonation of the Lisburne Group in the mature hydrocarbon kitchen to the south in the Colville Trough (J. W. Bielak and A. Brown, written comm. 1986; Chapter 3). WEST SAK FIELD West Sak Field solution gas is interpreted as biodegraded, based upon its dryness (> 98% methane), relatively high isobutane/n-butane ratio, the presence of isotopically heavy carbon dioxide and isotopically light methane, and propane that is isotopically heavier than either ethane or butane (Figure 1.22; Chapter 2). This isotopic reversal (i. e. ? 13Cpropane > ? 13Cbutane) is unusual and likely results from either mixing of gases from different sources (Chung et al., 1988) or from preferential removal of 12C during biodegradation (James and Burns, 1984; James, 1990; Rowe and Muehlenbachs, 1999; Burrus and Collett, 2000). Chapter 2 presents evidence that West Sak methane was generated by reduction of carbon dioxide under anaerobic conditions. PRUDHOE BAY FIELD The carbon isotopic composition of the Prudhoe Bay main field gas cap displays an altered isotopic pattern that is interpreted as a mixture of gases from different sources and/or thermal maturities. Propane is heavier than n-butane in Prudhoe main field gas, a relation originally noted by Chung et al. (1988) and attributed to mixing of gases from more than one source. If Prudhoe main field gas is an unaltered mixture from more than one source, however, its carbon isotopic composition should fall within the range of the other gases in the mixture. The isotopic composition of Prudhoe Bay ethane is heavier than ethane from any other gas on Figure 1.22 except for the biodegraded solution gas from the West Sak Field, so it is impossible to generate

23 the Prudhoe gas by mixing of these gases unless a biodegraded gas is included in the mixture. It is possible that gas delivered to the Prudhoe trap was generated at a higher maturity, with a heavier isotopic composition, than any of the other unaltered gases sampled to date. However, high-maturity gas should be enriched in isotopically heavy methane like the Lisburne gas tested from the 2F-20 well, but the methane in Prudhoe main field gas is lighter than the 2F-20 methane, possibly due to the presence of biogenic methane in Prudhoe gas. An alternative hypothesis of partial biodegradation of the Prudhoe gas charge is suggested by the similarity between the Prudhoe Bay main field gas cap and West Sak solution gas isotopic patterns. The isotopic pattern of heavy ethane/propane/butane and light methane for Prudhoe Bay gas is not as pronounced as the West Sak gas pattern, suggesting that the Prudhoe gas cap was either subjected to less biodegradation than West Sak gas, or that biodegraded Prudhoe gas was subsequently recharged and mixed with unaltered gas from the source kitchens. The gas from the Prudhoe Bay main field gas cap is wet (78% methane) and has an isobutane/n-butane ratio near the 0.5 average value of thermogenic gases that have not been biodegraded (Table 1.5; Alexander et al., 1983a). Nevertheless, the average C29 25-norhopane/C30 hopane ratio of 0.5 in Prudhoe Bay main field oils is higher than the ratios observed in any source rock extracts (Tables 1.2, 1.3) and provides evidence that biodegradation occurred in the Prudhoe trap at some time in the past (Figure 1.21). This postulated biodegradation event at Prudhoe Bay Field must have been followed by recharge of unaltered oil, because there is no evidence for biodegradation evident on gas chromatograms of Prudhoe Bay oils (Figure 1.21). Present-day temperatures of about 1000C at the Prudhoe Bay Field are at the upper limit tolerated by microorganisms that biodegrade oil (Connan, 1984), so any oil or gas biodegradation likely occurred when the Prudhoe trap was at shallower burial depths and lower temperatures. If mixing and/or biodegradation have affected the isotopic composition of Prudhoe Bay main field gas cap, it follows that it will be difficult to determine the co-sources of the gas. Because the Shublik Formation is interpreted as the main source of the oil at Prudhoe, it is logical to assume that most of the Prudhoe gas also was generated from the Shublik Formation, with possible lesser contributions of gas from HRZ and Kingak source rocks. An additional source of gas from the Lisburne Group carbonates is suggested by the 11% CO2 concentration and the relatively heavy carbon isotopic composition of 5.1 for carbon dioxide in the Prudhoe Bay main field gas cap (Figure 1.26). Gas tested from the Lisburne Group in the 2F-20 well has a high concentration of CO2, a CO2 isotopic composition near 0, and exhibits no evidence for mixing or alteration. Shublik carbonates could also in theory provide a source for inorganic CO2 in the Prudhoe gas cap, but the solution gases tested from Shublik-sourced oils at the Kuparuk Field and at the Kalubik #1 well exhibit CO2 concentrations less than 1% and carbon isotopic compositions of about 18 (Figure 1.26; Table 1.5). It could be argued that the Shubliksourced gases at Kuparuk Field and Kalubik #1 are not as mature as the 2F-20 Lisburne gas, and that the Shublik Formation carbonates may be capable of generating isotopically heavy CO2 at higher maturity levels. According to the method of James (1990), however, the maturities of the Kalubik #1 Shublik-sourced gas and the 2F-20 Lisburne gas are similar, although other evidence indicates a higher maturity for the 2F-20 gas (Figures 1.23, 1.24, and 1.25). The relatively light isotopic composition of the CO2 in Shublik-sourced oil is consistent with derivation from kerogen in Shublik source rock (Boreham et al., 1998). Isotopically light Shublik-sourced CO2 and isotopically heavy Lisburne-sourced CO2 define the end members of a

24 hypothesized mixing line that provides a plausible explanation for the intermediate isotopic compositions and CO2 concentrations observed in Prudhoe Bay main field gas, Prudhoe Bay Lisburne pool gas, and Point McIntyre Field gas (Figure 1.26). The higher concentration and heavier isotopic composition of CO2 in Lisburne pool gas relative to Prudhoe Bay main field gas is consistent with a mixing model, because the Lisburne reservoir should receive a higher proportion of self-sourced gas than the overlying Ivishak reservoir. The Lisburne pool and overlying Prudhoe Bay main field Ivishak reservoir share approximately the same fluid contacts and their gas compositions would be expected to have mixed and become identical over geologic time scales (Figure 1.4). The fact that Ivishak and Lisburne CO2 concentrations differ provides evidence that Lisburne-sourced gas is being delivered to the Lisburne pool faster than diffusion can mix the two gas caps. Carbon dioxide may be migrating to the Prudhoe Bay oil column from the Lisburne pool as dissolved gas in the underlying aquifer that is present beneath both pools (Figure 1.4). HRZ and Kingak source rocks may have also contributed some carbon dioxide to the Prudhoe Bay gas cap, but their contribution would be expected to be less than the Shublik contribution because Shublik is the predominant source of Prudhoe oils. Coals in the underlying Mississippian Kekiktuk Formation are another possible source of CO2, but organic matter in coal produces isotopically heavy CO2 only at high maturities (> 2.5% Ro; Boreham et al., 1998). The Kekiktuk coals probably were not deposited in the mature source kitchen south of Prudhoe Bay Field (Woidneck et al., 1987), and the maturity of the Kekiktuk interval in the Prudhoe Bay area is estimated to be less than 1.5% Ro. The Kekiktuk coals are therefore not likely to be the source of the isotopically heavy CO2 at Prudhoe. The gas mixing curve on Figure 1.26 suggests that 70% of the carbon dioxide in the Prudhoe Bay main field gas cap was generated from the Lisburne Group and 30% was generated from the Shublik Formation or from other isotopically light sources in the HRZ, Kingak, or Kekiktuk intervals. A 70% Lisburne contribution to Prudhoe Bay gas would amount to about 3.5 trillion cubic feet (TCF) of the total estimated 5 TCF of carbon dioxide that is present in the Prudhoe Bay gas cap and oil column. A carbon dioxide charge of this magnitude from the Lisburne Group must have been accompanied by a large methane charge as well, because 2F-20 Lisburne gas has a methane/CO2 molar ratio of about 4.5 (Table 1.5). If it is assumed that the 2F-20 gas composition is representative of the Lisburne gas charge to the Prudhoe trap, then the methane delivered to the Prudhoe trap from the Lisburne Group can be roughly estimated as 4.5 x 3.5 TCFCO2 = 16 TCFmethane, assuming that no CO2 has been lost from the Prudhoe trap. If it is further assumed that the isotopically light carbon dioxide was all generated from the Shublik Formation, then there must have been an enormous quantity of Shublik-sourced methane delivered to the Prudhoe trap. The methane/CO2 ratio of gas from Shublik-sourced oil at the Kuparuk Field and the Kalubik #1 well is about 100 (Table 1.5), so if the Shublik was the source of the remaining 1.5 TCF of carbon dioxide at Prudhoe, then the methane sourced from the Shublik Formation can be roughly estimated as 100 x 1.5 TCFCO2 = 150 TCFmethane. This estimate could be too low because of the assumption that no CO2 has escaped from the Prudhoe trap. The calculated contribution of 166 TCF of methane from Lisburne and Shublik sources must be increased by about 10%, to 183 TCF, to account for the additional quantity of ethane and

25 propane in the Prudhoe Bay gas cap (Table 1.5). The total calculated hydrocarbon gas charge of 183 TCF is much larger than the estimated 41 TCF of hydrocarbon gas in place in the Prudhoe gas cap and oil column, implying large losses of gas from the Prudhoe trap. The gas trapping efficiency, or proportion of gas charge retained in the Prudhoe Bay trap, can therefore be estimated as 41/183 ? 20%. The volume of gas in shallow hydrates trapped beneath the permafrost in the Prudhoe Bay and Kuparuk Field area is estimated to be 37 to 44 TCF (Figure 1.4; Collett, 1993a). Methane carbon isotopic compositions ranging from 50 to 39 in the hydrates are consistent with leakage and mixing of methane from the underlying Prudhoe Bay Field gas cap with shallow biogenic methane (Collett et al., 1988). Collett (1993b) estimates that 50 to 70 per cent of the methane within the shallow gas hydrates has migrated from the Prudhoe Bay gas cap. If it is assumed that 60%, or about 24 TCF, of the shallow gas hydrates leaked from the Prudhoe Bay Field, and that 142 TCF of gas leaked from the Prudhoe Bay gas cap, then about 17% of the leaked Prudhoe gas is now trapped as shallow gas hydrates. Some of this leaked gas could also biodegraded along with the oil. POINT MCINTYRE FIELD Gas compositions at the Point McIntyre Field provide further constraints on the timing and origin of the gas charge to the Prudhoe trap. The Point McIntyre gas cap is located about 2 miles (3.5 km) away from the bounding faults that separate the Point McIntyre Field from the Prudhoe Bay accumulation (Figure 1.20). The carbon isotopic composition of hydrocarbon gases at Point McIntyre Field is almost identical to Prudhoe Bay main field gases, suggesting a common origin for the hydrocarbon gas charge (Figure 1.22), but the concentration of carbon dioxide differs in the two fields. Carbon dioxide concentrations in Point McIntyre oils are highest at the southeastern part of the field nearest to the Prudhoe Bay bounding fault, and CO2 concentrations decrease to the north and west away from the Prudhoe Bay Field. These observations suggest that carbon dioxide may be diffusing across the bounding fault from the Prudhoe Bay or Lisburne Field oil columns into the Point McIntyre oil column. Alternatively, CO2 could be migrating up the faults from the Kekiktuk Formation or another deeper source other than the Prudhoe or Lisburne accumulations, but under this scenario it is difficult to explain why CO2 would preferentially migrate into the Prudhoe Bay and Lisburne Fields and somehow avoid the Pt. McIntyre Field. Diffusion coefficients of methane in oil are about twice as high as carbon dioxide diffusion coefficients (Grogan et al., 1986; Zhang et al., 1998), and the concentration of carbon dioxide in the Prudhoe Bay gas cap is about 1/7 the concentration of methane, so methane should diffuse into the Pt. McIntyre Field faster than carbon dioxide. England and Mackenzie (1989) suggested that an order of magnitude timescale estimate (in seconds) for lateral diffusion in hydrocarbon accumulations is given by 0.1L2 ? h2D-1 where L is the reservoir length (meters), D is the core C12 diffusion coefficient, and ? h? is the horizontal tortuosity (assumed to equal 1.0). Using England and Mackenzies diffusion coefficient of 1.7 x 10-10 m2/sec for C12 in core and a distance of 3.5 km from the Prudhoe Bay Field to the Point McIntyre gas cap, the order of magnitude time estimate for a C12 molecule to diffuse to the Point McIntyre gas cap is 230 million years (my). Because methane diffuses 100 times faster than decane through rock

26 (Leythaeuser et al., 1982), the time required for methane diffusion to the Point McIntyre gas cap would be reduced approximately two orders of magnitude to about 2 my. Because diffusion rates are roughly proportional to the molar concentration and inversely proportional to the square root of the molecular weight of the diffusing molecules, the diffusion rate of methane would be about 10 times faster than carbon dioxide: (0.43/0.07)* (44/16)-? ?? 10, where 16 is the molecular weight of methane, 44 is the molecular weight of carbon dioxide, 0.43 is the molar fraction of methane, and 0.07 is the molar fraction of carbon dioxide in Prudhoe Bay main field oils. These order-of-magnitude estimates suggest that CO2 will diffuse from the Prudhoe Bay Field to the Point McIntyre gas cap in about 20 million years, whereas methane will diffuse the same distance in about 2 million years. These estimates suggest that the CO2 charge reached the Prudhoe Bay main field gas cap in Tertiary time. The similarity between the isotopic compositions of Pt. McIntyre and Prudhoe Bay main field gases suggests that the isotopically heavy CO2 in Prudhoe gas reached the Prudhoe trap after the oil charge from the Shublik Formation. The geochemical similarities between Pt. McIntyre and Prudhoe Bay main field oils and gases indicate that the two fields experienced a similar filling history, and the oils in both fields are interpreted as predominantly sourced from the Shublik Formation. If the isotopically heavy CO2 charge came from the Shublik Formation at the same time as the oil charge, the Pt. McIntyre Field should have received it along with the Shubliksourced oil. KUPARUK FIELD Kuparuk Field oils were sourced predominantly from the Shublik Formation, but Kuparuk solution gas carbon isotopic compositions differ from Kalubik #1 and Prudhoe West End gases (Figure 1.22). If the Kalubik #1 and West End gases are sourced from the Shublik Formation, as hypothesized above, it is necessary to invoke either higher maturity, different source facies, and/or biodegradation of Kuparuk Field gas in order to explain the heavy ethane/propane composition and light methane composition of Kuparuk Field gases relative to other Shubliksourced gases. The presence of C29 25-norhopane in all Kuparuk Field oils provides independent evidence for biodegradation, although the C29 25-norhopane/C30 hopane ratios in Kuparuk oils are not much higher than some of the ratios in source rock extracts (Tables 1.2, 1.3; Figure 1.21). In contrast, the Kalubik #1 oil has no measurable C29 25-norhopane concentration, which is consistent with the interpretation that its solution gas has not been altered by biodegradation. The C29 25-norhopane/C30 hopane values in all the source rock extracts are < 0.02, with the exception of PBU 12-03 extracts, which have relatively high S1/TOC values suggestive of contamination by Prudhoe crude (Tables 1.1, 1.2). The C29 25-norhopane/C30 hopane ratio increases from < 0.01 in Kalubik #1 oil to an average value of 0.03 in Kuparuk Field oils, an average value of 0.05 in Prudhoe Bay main field oils, and an average value of 0.1 in West Sak oils (Table 1.3; Figure 1.21). The systematic increase in biodegradation suggested by the 25norhopane concentration in the oils is directly correlated with the systematic 13C enrichment in ethane, propane, and n-butane that is observed in Kuparuk Field, Prudhoe Bay main field, and West Sak Field gases on Figure 1.22. Although this relation does not prove that these gases have been biodegraded, it provides evidence that biodegraded gases may have been mixed with other unaltered gases.

27 It is also possible to generate the Kuparuk Field gas isotopic compositions by mixing unaltered gases from different sources and maturities, but this scenario does not account for the evidence for slight biodegradation in the Kuparuk Field oils. If it is argued that the Kuparuk Field gas was generated at higher maturity than the other Shublik-sourced oils, then its isotopically light methane is difficult to explain, because methane in a high-maturity gas should be isotopically heavier than in a low-maturity gas from the same source (Clayton, 1991). It is possible that Kuparuk Field gases were generated at higher maturities, and heavier isotopic compositions, than the Kalubik #1 and West End Shublik-sourced gases, and that the relatively light isotopic composition of Kuparuk Field methane resulted from a later addition of biogenic methane. TARN AND ALPINE FIELDS The carbon isotopic compositions of Tarn and Alpine gases suggest a mixture of isotopically light, biogenic methane and heavier thermogenic gas (Figure 1.22). It would be logical to expect that the thermogenic component of Tarn gas is sourced from the HRZ Formation that sourced Tarn oil, and that the thermogenic component of Alpine gas is sourced from the Kingak Shale that sourced Alpine oil. However, the isotopic compositions of ethane, propane, and n-butane in Tarn and Alpine gases are similar to the Prudhoe West End and Kalubik #1 gases that are interpreted as sourced from the Shublik Formation (Figure 1.22). HRZ-sourced gas would be expected to be isotopically heavier than Shublik-sourced gas at equivalent maturity because HRZ-sourced oils and kerogen are isotopically heavier than Shublik-sourced oils and kerogen (Figure 1.12). Gas from the Umiat #8 well is isotopically heavier than Kalubik #1 Shubliksourced gas, as expected, since Umiat #4 oil is isotopically heavier than Shublik-sourced oils (Table 1.5). Similar logic would apply to Kingak-sourced gases, which would be expected to be lighter than Shublik-sourced gases because Kingak-sourced oils are isotopically lighter than Shublik-sourced oils (Figure 1.12). The similarity of ethane and propane isotopic compositions in Alpine and Tarn gases to Shubliksourced gases suggests the possibility that Tarn oil is a mixture of HRZ-sourced oil and Shubliksourced thermogenic gas, and that Alpine Field oil is a mixture of Kingak-sourced oil and Shublik-sourced thermogenic gas, with additional biogenic methane in both fields. The relatively light hydrogen isotopic composition of 227 in Alpine Field methane is consistent with a mixture of thermogenic and biogenic gas (Table 1.5; Whiticar et al., 1986). Temperatures at Alpine and Tarn fields are less than 750C, within the range tolerated by microorganisms that biodegrade oil. There is a small gas cap at Tarn Field, but Alpine oils are undersaturated and there is no gas cap at Alpine Field. The maturity of the Shublik Formation is estimated to be about 1.2% Ro beneath Alpine and Tarn Fields (Chapter 3), so gas could have been generated from Shublik source rock beneath both fields at the same time that the shallower, less mature Kingak and HRZ source rocks were generating oil. It must be acknowledged, however, that interpretations based upon the gas isotope data are equivocal because of the interpretation required to identify end member gases, the possibility of mixed gases and alteration, and the effect of maturation on the gas isotopic composition.

28 CONCLUSIONS 1. The Shublik Formation is the richest source rock in the central North Slope and is the source of intermediate-gravity (< 270 API), moderate-sulfur (> 0.6% S) oils. Kuparuk Field oils were sourced from the Shublik Formation. Prudhoe Bay main field oils were predominantly sourced from the Shublik Formation (~60% Shublik co-source) with an additional 40% co-source from the HRZ Formation and the Kingak Shale. 2. Oils sourced from HRZ Formation and Kingak Shale marine shales have higher API gravities (> 350) and lower sulfur contents (< 0.3% S) than Shublik-sourced oils. An HRZ source is interpreted for Tarn Field oils and a Kingak source is interpreted for the Alpine Field oils. 3. Gas cap core extracts suggest that a mixed oil charge from Shublik, Kingak, and HRZ sources reached the Prudhoe Bay main field before the main gas charge. 4. The geochemical differences between Prudhoe Bay main field and West End gases and oils indicate that the West End experienced a separate filling history from the main field. 5. Prudhoe Bay main field oils spilled into the West Sak Field and were biodegraded. Geochemical evidence indicates that the spillage did not occur along the Eileen fault, and that Prudhoe oils did not spill into the Kuparuk Field. 6. Oils from the Kuparuk Field and the Prudhoe Bay main field show evidence for biodegradation during their filling histories. 7. Gases from the Tarn and Alpine Fields exhibit carbon isotopic compositions that are consistent with a mixture between Shublik-sourced thermogenic gas and biogenic methane. 8. Carbon dioxide in the Prudhoe Bay, Lisburne, and Pt. McIntyre gas caps was likely cosourced primarily by the Shublik Formation and the Lisburne Group, with possible additional contributions from the HRZ Formation, Kingak Shale, and Kekiktuk Formation. Lisburne Group CO2 could have been generated at temperatures exceeding 1500C in the Colville Trough to the south. Order-of-magnitude estimates suggest that 80% of the hydrocarbon gas charge has escaped from the Prudhoe Bay trap. 9. Oil in the Pt. McIntyre Field is geochemically similar to Prudhoe Bay main field oil, indicating the same co-sources in approximately the same proportions. Carbon dioxide in the Pt. McIntyre Field increases in concentration towards the Prudhoe bounding fault, possibly indicating diffusion of CO2 from Prudhoe Bay and/or Lisburne accumulations into the Pt. McIntyre Field. 10. The Prudhoe Bay tar mat likely resulted from gas deasphalting by a CO2-rich gas charge at the base of a gravity-segregated oil column in the highly porous and permeable Ivishak Sandstone reservoir.

29 CHAPTER TWO EVIDENCE FOR BIODEGRADATION AND EVAPORATIVE FRACTIONATION IN WEST SAK, KUPARUK, AND PRUDHOE BAY FIELD AREAS INTRODUCTION Geochemical data presented in Chapter 2 provide evidence for the hypothesis that oils in the West Sak Field on the North Slope of Alaska are a mixture of biodegraded oil spilled from the Prudhoe Bay Field and gas/condensate leaked from the underlying Kuparuk Field by the process of evaporative fractionation. West Sak oils have been moderately to heavily biodegraded and have lost essentially all normal alkanes and isoprenoids in their C15+ fraction, yet also contain anomalously high concentrations of gasoline-range saturate and aromatic compounds that are not expected to persist at this level of biodegradation (Peters and Moldowan, 1993; Connan, 1984). Gas chromatography/isotope ratio mass spectrometry (GC/IRMS) analyses of fourteen West Sak, Kuparuk, and Prudhoe Bay oils are interpreted to indicate that the anomalous West Sak gasolinerange compounds migrated vertically into the West Sak reservoir from the underlying Kuparuk reservoir, and were then subjected to light biodegradation in the shallowest West Sak reservoirs. This model has exploration implications for other areas of the world where shallow biodegraded oil accumulations with anomalous gasoline-range compounds may indicate the presence of a deeper, undiscovered petroleum accumulation that provided the secondary condensate charge (e. g. Dzou and Hughes, 1993; Holba et al., 1996). The research reported in this chapter builds upon Leon Dzou and Albert Holba's research into the origin of Prudhoe Bay, Kuparuk, and West Sak Field oils. In 1993, Dzou and Masterson coauthored a report citing evidence for evaporative fractionation and leakage of a gas and condensate charge from the Kuparuk Field into the overlying West Sak Field. The bulk of Chapter 2 consists of subsequent research conducted solely by the author, including the isotopic compositions of C6 and C7 hydrocarbon compounds in West Sak, Kuparuk, and Prudhoe Bay Fields, geochemical evidence for biodegradation of the secondary condensate charge and solution gas in the shallowest West Sak reservoirs, isotopic correlation of the secondary condensate charge to the Kuparuk Field, interpretation of the isotopic fractionation factors for evaporative fraction and CO2 reduction, evidence for anaerobic biodegradation and lack of water washing, the relative resistance of C6 and C7 compounds to biodegradation, discussion of alternative hypotheses for the geochemical data, and implications for development of West Sak oil reserves. Ann Fincannon operated and maintained the GC/IRMS instrument used to obtain the carbon isotopic data at ARCO, and she and the author calculated the isotopic compositions of individual compounds from the raw experimental data. Leroy Ellis and Ann Fincannon co-authored a patent for a capillary furnace tube in the GC/IRMS instrument that significantly improved the quality of the isotopic measurements. Chapter 2 has been accepted for publication by the journal Organic Geochemistry as "Evidence for Biodegradation and Evaporative Fractionation in West Sak, Kuparuk, and Prudhoe Bay Field Areas, North Slope, Alaska" by Masterson, Dzou, Holba, Fincannon, and Ellis.

30 SYNOPSIS Oils from the West Sak, Kuparuk, and Prudhoe Bay Fields on the North Slope of Alaska display geochemical evidence for a complex petroleum filling history that includes multiple sources and alteration by evaporative fractionation and biodegradation. Source-specific biomarkers in West Sak oils indicate generation from the same source rocks in approximately the same proportions as Prudhoe Bay Field oil, consistent with the hypothesis that oil spilled from the deeper Prudhoe accumulation and remigrated about 10 miles laterally and 5000 feet vertically into the West Sak Field. West Sak oils are moderately biodegraded but exhibit anomalously high concentrations of gasoline-range saturate and aromatic compounds that are interpreted as a secondary gas/condensate charge that arrived after biodegradation of the spilled Prudhoe oil. The shallowest West Sak oils have less secondary gas/condensate charge, lower API gravities, and reduced concentrations of methylcyclopentane, benzene, cyclohexane, 3-methylhexane, heptane, methylcyclohexane, and toluene relative to the deepest West Sak zone A oils. The carbon isotopic compositions of these C6 and C7 compounds in the shallowest West Sak reservoirs are heavier than the deepest West Sak oil reservoirs by up to 3 and the isotopic compositions of saturate compounds are altered more than those of aromatic compounds. The heavier isotopic compositions of C6 and C7 compounds in the shallow West Sak reservoirs are interpreted to result from a kinetic isotope shift caused by light biodegradation of the secondary gas/condensate charge. West Sak Field solution gas is also interpreted as biodegraded, based upon its dryness (> 98% methane), relatively high isobutane/n-butane ratio, the presence of isotopically heavy carbon dioxide and isotopically light methane, and propane that is isotopically heavier than either ethane or butane. The isotopic compositions of methane and carbon dioxide in West Sak gas suggest that biogenic methane was generated during CO2 reduction under anaerobic conditions. The isotopic compositions of C6 and C7 compounds in the deepest, least biodegraded West Sak oils are nearly identical to the underlying oils from the Kuparuk Field but differ from the Prudhoe Bay Field oils. The Kuparuk Field is therefore postulated as the source of the secondary gas/condensate charge observed in oils from the West Sak Field. Ratios of toluene/heptane and heptane/methylcyclohexane in Kuparuk oils provide independent evidence for loss of gas and condensate from the Kuparuk reservoir by the process of evaporative fractionation, and the oils subjected to the most evaporative fractionation are isotopically heavier in the C6-C7 range. The isotopic compositions of West Sak zone A C6 and C7 hydrocarbons suggest that a slight (~0.8) isotopic fractionation resulted from evaporative fractionation of the gas/condensate charge from the Kuparuk Field oil accumulation. North/northeast-striking faults that connect the Kuparuk and West Sak reservoirs provide a potential migration pathway for the secondary gas/condensate charge through 3000 feet of intervening shale. This model of West Sak oil biodegradation, subsequent secondary gas/condensate charge, and further biodegradation has implications for development of North Slope West Sak oil reserves, because heavily biodegraded West Sak oils that lack a secondary gas/condensate charge may be too viscous to develop by conventional waterflooding methods. GEOLOGICAL SETTING The Kuparuk, West Sak, and Prudhoe Bay Fields are located about 250 miles (400 kilometers) north of the Arctic Circle on the coastal plain of the North Slope of Alaska between the NPRA

31 and the ANWR (National Petroleum Reserve in Alaska and Arctic National Wildlife Refuge; Figure 1.1). The Kuparuk Field is a combination of a structural and stratigraphic trap in Lower Cretaceous marine sandstones (Figures 1.3, 1.4) at about 6,000 feet (1,829 meters) subsea depth with an oil column height of about 1,000 feet (300 meters). It produced at an average rate of about 230,000 barrels of oil per day (BOPD; 37,000 cubic meters per day) in 1999 and is the second most productive field in the United States after the Prudhoe Bay Field. The Kuparuk Field covers an area of about 265 square miles (675 square kilometers) immediately west of Prudhoe Bay and originally held 6 billion stock tank barrels (950 million cubic meters) of oil in place, with ultimate recovery expected to exceed 2 billion barrels (300 million cubic meters; BP and ARCO, 1997). Kuparuk oil has an average gravity of 240 API with a sulfur content of 1.4 to 2 percent and an average reservoir temperature of 680C (Masterson and Eggert, 1992). The original Kuparuk reservoir pressure was 3,135 pounds per square inch (psi; 21,615 kilopascals) at 6,000 feet (1,829 meters) subsea depth. The Kuparuk Field had no gas cap when it was discovered and the oil was undersaturated with a bubble point of approximately 2,900 psi (20,000 kilopascals). The West Sak Field is a shallow, biodegraded oil accumulation between 2,000 and 4,000 feet (600 and 1,200 meters) in Upper Cretaceous marine sandstones of the Schrader Bluff Formation in the Kuparuk River Unit (KRU; Figures 2.1, 2.2). At least 15 billion barrels (2.4 billion cubic meters) of oil in place are believed to be trapped in the West Sak sands over an area of 200 square miles (500 square kilometers) that mostly overlies the Kuparuk Field (Werner, 1987; Figure 1.1). Oil at the West Sak Field is trapped in numerous fault blocks bounded by north/northeast-striking faults that displace both the West Sak and underlying Kuparuk reservoirs (Figures 2.1, 2.2). Except for a pilot waterflood test conducted from 1984 until 1986, no oil was produced from the West Sak Field prior to 1997 because of its relatively high viscosity, which ranges from 26 to 3,000 centipoise at reservoir conditions. In late 1997, development of the West Sak Field commenced with production of 1,000 BOPD (160 cubic meters per day) from three wells in a sweet spot overlying the eastern part of the Kuparuk Field (Foerster et al., 1997). The West Sak reservoir in this area produces oil ranging from 17 to 210 API gravity and 26 to 67 centipoise viscosity at a depth of 3,500 to 4,000 feet (1,000 to 1,200 meters) subsea and a temperature of about 250C. The least viscous oils, which also have the highest API gravities, are produced from the deepest sand intervals in the West Sak reservoir. The original West Sak reservoir pressure was about 1,550 psi (10,690 kilopascals) at 3,650 feet (1,113 meters) subsea depth. The Prudhoe Bay Field is located immediately east of the Kuparuk Field and is the largest oil field in the United States, with an estimated 25 billion stock tank barrels (4 billion cubic meters) of original oil in place and 46 trillion standard cubic feet (1.3 trillion cubic meters) of gas in place in the original gas cap and in solution with the oil (Figure 1.1; BP and ARCO, 1997). The main reservoir in the Prudhoe Bay Unit (PBU) is Triassic Ivishak sandstone at about 8,800 feet (2,700 meters) subsea depth (Figures 1.3, 2.2). The trapping mechanism is a combination of a fault-assisted structural closure and stratigraphic truncation of the Ivishak reservoir by a Lower Cretaceous unconformity on the eastern side of the field (Figure 2.2; Jamison et al., 1980). At field discovery, the maximum oil column was about 450 feet (140 meters) thick and the maximum gas cap was about 400 feet (120 meters) thick (Figure 1.4). Prudhoe Bay Field produced at an average rate of about 550,000 BOPD (87,000 cubic meters per day) in 1999 and

32 ultimate recoverable reserves are expected to exceed 13 billion barrels (2 billion cubic meters; BP and ARCO, 1997). The original reservoir temperature varied from 80 to 1100C across the 30mile (50-kilometer) length of the field, and the average oil gravity is 290 API. METHODS SAMPLES Six oils from the West Sak Field, four oils from the Kuparuk Field, and four oils from the Prudhoe Bay Field were analyzed by gas chromatography-isotope ratio mass spectrometry (GC/IRMS; Figures 2.1, 2.3; Tables 2.1, 2.2). Twelve oils and four source rocks were analyzed by gas chromatography-mass spectrometry (GC/MS) and gas chromatography-tandem mass spectrometry (GC/MS/MS; Figures 2.1, 2.4, 2.5). The West Sak oils were recovered from production tests in the West Sak A, B, and D reservoir zones in the West Sak Pilot (WSP) 8I and West Sak (WS) 1-01 wells in the southeastern part of the Kuparuk Field. Oil gravities are highest in Zone A, the deepest West Sak reservoir, and decrease upwards to lower gravities in Zones B and D (Table 2.1). The four Kuparuk Field oils analyzed by GC/IRMS were recovered from the two principal reservoirs in the field: the C sandstone reservoir (wells 2W-12 and 1D-04) and the A sandstone reservoir (wells 2W-12 and 1E-11). The 1E-11 and 1D-04 wells are located in the southeastern part of the Kuparuk Field near the locations of the West Sak production wells (Figure 2.1). Twenty-three Kuparuk Field bottomhole sampled oils were also analyzed by whole-oil gas chromatography, including 19 tests from A sandstones and 4 tests from C sandstones over the entire field area. Two of the Prudhoe Bay oil samples were tested from the West Kuparuk 3-11-11 well in the western part of the Prudhoe Bay Unit known as the Eileen/West End area (Figures 2.1, 2.2). One oil sample was tested from the Ivishak formation, which is the main producing reservoir at Prudhoe, and the second was tested from a shallower Kuparuk reservoir that has not been produced. The Kuparuk reservoir in the 3-11-11 well is located less than 1,000 feet (300 meters) away from the Eileen fault (Figures 2.1, 2.2) that Carman and Hardwick (1983) suggested was the vertical migration conduit for spillage of Prudhoe oil into the overlying Kuparuk reservoir. Two additional Prudhoe Bay Field oil samples came from the main Ivishak reservoir at Drill Site 4-05 in the northeastern part of the field and Drill Site 17-01 in the southeastern part of the field (Figure 2.1). Solution gas from West Sak Field was sampled at the surface from the 1D-125, 1D-126, and 1D129 producing wells, which are located near the WS 1-01 well. All three wells produce comingled oils from zones A, B, and D, so the solution gas is a mixture that cannot be allocated to an individual reservoir zone. Gas chemical and isotopic compositions were measured by ISOTECH Laboratories in Champaign, Illinois. SAMPLE PREPARATION Oil and rock samples were prepared at ARCO Exploration and Production Technology and at Baseline Resolution Inc. in Plano, TX. Source rock samples were crushed and extracted with methylene chloride in a Soxhlet apparatus. Oil samples for GC/MS and GC/MS/MS analyses

33 were topped under a stream of nitrogen at 400C for one hour and excess pentane was added to precipitate asphaltenes. Oil samples for GC and GC/IRMS analyses were stored in a freezer and were not topped. The polar fraction was removed using a Waters Sep-Pak Plus CN cartridge with pentane solvent. The saturated hydrocarbon fraction was separated by medium-pressure liquid chromatography (MPLC) using deactivated silica and activated silica columns. WHOLE OIL GAS CHROMATOGRAPHY (GC) Whole oils were spiked with trans-2-heptene as an internal standard and analyzed on a Hewlett Packard 5890 Series II gas chromatograph. The concentrations reported in Table 2.3 were calculated by multiplying the internal standard concentration by the ratio of the unknown peak area to the peak area of the internal standard. The data were processed using EZ Chrom software from Scientific Software Inc. Analytical conditions are documented in Dzou and Hughes (1993). GAS CHROMATOGRAPHY-MASS SPECTROMETRY (GC/MS) The aliquot of saturate fraction for GC/MS analysis was diluted with cyclohexane and spiked with 5? -cholane as an internal standard. Ortho-biphenyl was used as the internal standard for the aromatic fraction. The analysis was performed on a Hewlett Packard 5890 Series II gas chromatograph that is coupled to a Hewlett Packard 5970 Series mass selective detector. Analytical conditions are documented in Hughes and Dzou (1995). GAS CHROMATOGRAPHY-MASS SPECTROMETRY-MASS SPECTROMETRY (GC/MS/MS) Saturate fractions were analyzed by GC/MS/MS in the MRMQ mode using a VG AutoSpec Q tandem mass spectrometer coupled to a Hewlett Packard 5890 Series II gas chromatograph equipped with an on-column injector and fitted with a J&W Scientific DB-1 fused silica capillary column (60 m x 0.25 mm I. D., 0.25 ? m film thickness). Helium was the carrier gas at 30 psi constant pressure and the column was heated from 150 3000C at 20C/min, with a final hold at 3000C for 30 minutes. Argon was used as the collision gas at a collision energy of 25 V and a cell pressure of 1E-6 mbar. Data were acquired and processed using the OPUS system. GAS CHROMATOGRAPHY-ISOTOPE RATIO MASS SPECTROMETRY (GC/IRMS) Whole oil samples for GC/IRMS analyses were not topped and were stored in sealed vials in a freezer until they were analyzed. Methylcyclopentane, benzene, cyclohexane, 3-methylhexane, heptane, methylcyclohexane, and toluene were selected for GC/IRMS analyses because they are relatively abundant in all the oils and are generally free of co-elutions (Figure 2.3). However, the isotopic compositions of methylcyclopentane and methylcyclohexane could be affected by other less abundant compounds that co-elute, or nearly co-elute, on the DB-1 column. The analyzed compounds are less volatile, and therefore less likely to have been evaporated and isotopically fractionated by sample handling, than hexane and lighter compounds in the oil. Whiticar and Snowdon (1999) report that compounds heavier than pentane in whole oils do not experience significant isotopic shifts due to evaporation unless they are stored open at room temperature for long periods of time.

34 Two aliquots of oil from zones B/A4 in the WSP 8I well were prepared and analyzed separately to test for the possibility that variation in sample handling at room temperature might affect the experimental results. Compounds such as 3-methylhexane, methylcyclohexane, and toluene that are present in concentrations greater than 0.1% (1 part per thousand) in the B/A4 oil exhibit good reproducibility, with an average isotopic difference of 0.2 between the two aliquots (Tables 2.2, 2.3). Reproducibility is not as good for methylcyclopentane, benzene, cyclohexane, and heptane, which are present in concentrations less than 0.1% and exhibit an average difference of 0.6 between the two aliquots. I conclude that sample handling did not significantly affect the experimental results, but recognize that experimental errors are higher for compounds present in concentrations less than 0.1%. Experimental error also appears to be related to the volatility of the compounds, because the average standard deviations for all the oils in the study are highest for methylcyclopentane and benzene and lowest for methylcyclohexane and toluene (Table 2.2). The average standard deviation calculated from triplicate analyses is 0.24 and varies from 0.29 for benzene down to 0.2 for methylcyclohexane. All carbon isotopic compositions are reported relative to PDB. Whole oils were analyzed with a Hewlett-Packard 5890 gas chromatograph equipped with a model 7673 automatic cool on-column injector system in tandem with a Model SIRA II (MicroMass UK) isotope ratio monitoring mass spectrometer. A fused silica column of 60 m x 0.25 mm ID coated with DB-1 stationary phase (J&W Scientific) was used for all analyses. Helium was used as carrier gas at a linear gas velocity of 33 cm s-1. The GC oven was programmed from 30C (5 min. hold time) to 50C at 3C min-1, then from 50 to 310C (20 min. hold time) at 10C min-1. The combustion furnace was maintained at 900C. Typical MS operating conditions were: ionization energy 100 eV; trap current 600A; accelerating voltage 2550 KV. Further details about GC/IRMS configuration are provided in Ellis and Fincannon (1998). OIL-SOURCE ROCK CORRELATION Previous publications presented evidence that three source rocks contributed to the Prudhoe accumulation (Figure 1.3): Triassic marine limestone, shale, and phosphorite (Shublik Formation), Jurassic marine shale (Kingak Shale), and Lower Cretaceous marine shale (HRZ Formation, also known as the gamma ray zone or pebble shale; Seifert et al., 1980; Magoon and Claypool, 1981; Claypool and Magoon, 1985; Premuzic et al., 1986; Sedivy et al., 1987; Bird, 1994). Of these three potential source rocks, the Shublik Formation is the only source capable of generating oils with high concentrations of tricyclic terpanes (Figure 2.4). Since Prudhoe, West Sak, and Kuparuk oils all contain higher tricyclic terpane concentrations than either Kingak or HRZ source rock extracts at oil window maturities, all three oils must have had a significant Shublik source component (Figure 2.5). The relatively high sulfur content of Prudhoe, Kuparuk, and West Sak oils (0.6 2% S; Table 2.1) is also consistent with a large Shublik carbonate source contribution. Oils thought to have been sourced from either the Kingak or HRZ shales, for example Kavearak Point #1 and Umiat oils, have sulfur concentrations less than 0.4% (Magoon and Claypool, 1981; Magoon and Claypool, 1984; Premuzic et al., 1986) A 24-nordiacholestane biomarker that is present in relatively high concentrations in HRZ source rock extracts is also present in Prudhoe and West Sak oils (NDR ratio, Tables 1.2, 1.3; Holba et

35 al., 1998). Kingak and Shublik source rock extracts contain much lower concentrations of 24nordiacholestane and have average NDR values of 0.1, compared to a NDR value of 0.6 for HRZ source rock in the Badami #1 well (Figure 1.1, Table 1.2). Oils with NDR ratios greater than 0.2 are interpreted as sourced or co-sourced from HRZ source rock. The 0.15 NDR ratio in KRU 1D04 and other oils from the Kuparuk Field indicates that the Kuparuk Field accumulation did not receive any volumetrically significant HRZ contribution. HRZ source rock is immature in the Kuparuk Field area and is stratigraphically separated from the underlying Kuparuk reservoir by 100 feet (30 meters) of intervening Kalubik Formation shale (Figures 1.3, 1.4; Magoon and Bird, 1985; Carman and Hardwick, 1983). In order for Prudhoe and West Sak oils to have similar biomarker signatures (Figure 2.5), they must have been generated from the same source rocks in approximately the same proportions. It would be extremely fortuitous for West Sak oils to have been co-sourced by the same three source rocks in the same proportions as Prudhoe oils. The Prudhoe Bay reservoir is in direct contact with all three of the source rocks, but the West Sak reservoir is not in contact with any of the source rocks (Figure 2.2). The oil accumulations in West Sak reservoirs are observed to stairstep downdip to the east for about 10 miles (16 kilometers) until they reach the western area of the Prudhoe Bay Field where spillage of the Prudhoe accumulation occurred (Figure 2.2). The most plausible scenario in which the biomarker signatures of West Sak oil could so closely resemble biomarkers in Prudhoe oil is by remobilization of a previously mixed Prudhoe oil that spilled from the Prudhoe trap and remigrated approximately 10 miles (16 kilometers) laterally and 5,000 feet (1,525 meters) vertically into the West Sak Field (Figure 2.2). The slightly elevated sulfur concentration and lower API gravity of West Sak oil relative to Prudhoe oil can be attributed to biodegradation, which would result in preferential removal of alkanes and aromatic compounds from West Sak oil with a corresponding increase in the relative concentrations of sulfur-rich asphaltene and polar compounds. The increased sulfur content in West Sak oils relative to Prudhoe Bay oils could alternatively result from a higher proportion of Shublik-sourced oil, or another sulfur-rich source rock facies, in West Sak oil. However, the ranges of source-diagnostic biomarker ratios such as tricyclic terpane/hopane and NDR are similar in West Sak and Prudhoe Bay Ivishak oils, suggesting approximately equal Shublik cosource proportions (Table 1.3). Oil produced from the Kuparuk River Field has a distinctive biomarker signature that corresponds to a distal, organic-rich facies of the Shublik Formation that was penetrated in the Phoenix #1 well northwest of the Kuparuk Field (Figures 2.1, 2.4, 2.5e). Kuparuk oils have a higher sulfur content than Prudhoe oils, consistent with biomarker evidence for lack of an HRZ co-source to dilute the high-sulfur Shublik contribution in Kuparuk Field oils (Tables 1.3, 2.1). The high C29/C30 hopane ratio in Kuparuk Field crude is also consistent with a carbonate-rich source rock like the Shublik facies penetrated by the Phoenix well (Peters and Moldowan, 1993; Robison et al., 1996). Carman and Hardwick (1983) presented a migration model in which oil spilled from the Prudhoe reservoir into the Kuparuk and West Sak reservoirs during an eastward Tertiary tilting event on the North Slope. Masterson and Paris (1987) suggested that Tertiary tilting resulted from crustal loading caused by thrusting in the Arctic National Wildlife Refuge (ANWR) 160 miles (250

36 kilometers) east of the Prudhoe Bay Field, and that north/northeast-striking faults formed in response to the eastward tilting in the Kuparuk Field area (Figure 2.1). Geochemical evidence reported in Chapter 1 supports the hypothesis that Prudhoe Bay oil spilled into the West Sak reservoir, but does not support Carman and Hardwicks suggestion that Prudhoe oils also spilled into the Kuparuk Field. The Kuparuk Field oils have a unique biomarker signature, higher sulfur content, and lower API gravity than Prudhoe Bay oils. EVIDENCE FOR BIODEGRADATION OF WEST SAK FIELD OILS AND GASES On the Peters and Moldowan (1993) numerical scale of biodegradation, the West Sak oils are classified as moderately to heavily degraded (ranks 5 to 6) in their heavy end but only lightly degraded (rank 1) in their light end (Figure 2.5a). The C29 17? ,25-norhopane/C30 17? -hopane ratio in the West Sak oils increases from 0.08 in West Sak zone A reservoirs up to 0.12 in the shallower D zone, consistent with moderate to heavy biodegradation (Moldowan and McCaffrey, 1995; Table 1.3). The anomalous presence of light, gasoline-range paraffins and aromatic compounds in West Sak oil suggests that a second charge of gas and condensate postdated the biodegradation and removal of the heavier paraffins and isoprenoids. Solution gas from the West Sak Field displays geochemical evidence for alteration by biodegradation. Gas samples were analyzed from three development wells near the West Sak 101 well. These wells produce oil from all three West Sak reservoirs, so the gases represent a combination from zones A, B, and D in unknown proportions. Geochemical allocation of the oil production from the three wells suggests that most of the solution gas produced from these wells is coming from zones B and D (M. McCaffrey, written comm. 2000). West Sak Field solution gas is dry, consisting of than more than 98% methane, and the carbon isotopic composition of West Sak methane is relatively light (-49), consistent with the presence of biogenic gas (Table 1.5; Schoell, 1983). The isotopic compositions of West Sak methane and carbon dioxide are consistent with methanogenesis by reduction of CO2 in an anaerobic environment. West Sak carbon dioxide has a relatively heavy carbon isotopic composition (d13C = +13.8). West Sak methane and formation waters have a relatively light hydrogen isotopic composition (dDmethane = -304 and dDwater = -141). Different methanogenic pathways can be distinguished by the carbon isotopic fractionation factor dC(CO2/CH4) = (1000 + d13C[CO2])/(1000 + d13C[CH4]) = 1.066 and the hydrogen isotopic fractionation factor dD(H20/CH4) = (1000 + dD[H20])/(1000 + dD[CH4]) = 1.23 between West Sak methane, carbon dioxide, and formation water. These isotopic fractionations suggest that West Sak methane formed by reduction of carbon dioxide (Figure 2.6; Whiticar et al., 1986). The hydrogen isotopic composition of West Sak formation water is extremely light due to flushing by depleted meteoric water from the surface at high latitude. If the isotopically light composition of West Sak formation water is not taken into account, the hydrogen isotopic composition of West Sak methane could be misinterpreted as evidence for methanogenesis by acetate fermentation in the genetic classification diagrams published by Whiticar et al. (1986) and Kaplan (1994). At the average West Sak reservoir temperature of 250C, the calculated carbon isotopic exchange equilibrium value of ? between methane and carbon dioxide is 1.071 (Richet et al., 1977;

37 Whiticar et al., 1986; 102 ln cT = 2.92(1000/0K) 2.96), similar to the value of 1.066 observed in West Sak solution gas. Reduction of carbon dioxide occurs in an oxygen-free environment, indicating that West Sak methane was likely generated under anaerobic conditions (Whiticar et al., 1986; Kaplan, 1994). Because water is thought to provide the source of hydrogen for reduction of CO2 to methane (Whiticar et al., 1986), the biogenic methane was likely generated at downdip oil-water contacts in the West Sak sands and migrated up into the oil column. Propane in West Sak solution gas is isotopically heavier than both ethane and n-butane (Figure 2.7). This isotopic reversal (i. e. 13Cpropane > 13Cbutane) is unusual and likely results from either mixing of gases from different sources (Chung et al., 1988) or from biodegradation (James and Burns, 1984; Rowe and Muehlenbachs, 1999). Lebedew et al. (1969) demonstrated that bacterial oxidation can enrich 13C in propane by 5 under laboratory conditions. The isotopic compositions of ethane, propane, and butane in West Sak gases are 2 - 4 heavier than in the underlying Kuparuk Field gases (Figure 2.7). Because 12C - 12C bonds require less energy to break than 12C - 13C bonds, biodegradation of West Sak ethane, propane, and butane should preferentially concentrate the 13C isotope, causing a kinetic isotope shift (Stahl, 1977; Chung et al., 1988) to heavier isotopic compositions. Biodegradation of West Sak gas is also suggested by the ratio of isobutane/n-butane of about 0.8, significantly higher than the ratio of 0.5 in most thermogenic gases (Alexander et al., 1983a) and in Kuparuk Field gas (Table 1.5). Isobutane is biodegraded at a slower rate than n-butane (Bopp et al., 1981). High ratios of isobutane/n-butane can also be generated at high source rock maturity (Prinzhofer et al., 2000), but maturity-sensitive biomarker ratios such as Ts/Tm and condensate-range compound ratios such as the Heptane and Isoheptane Values (Thompson, 1979, 1983) provide no evidence for high maturity of West Sak oils and gases (Figure 2.5; Tables 1.3, 2.4). Maximum West Sak reservoir temperatures of 38C are well below the 80-90C upper limit tolerated by microorganisms that biodegrade oil (Werner, 1987; Palmer, 1993; Connan, 1984). Water salinities decrease to as little as 3,000 ppm in the western, updip part of the West Sak Field. Oil gravities in the West Sak accumulation also decrease updip, as would be expected if increased biodegradation is associated with exposure to fresh, oxygenated meteoric water recharge from the surface. At present, meteoric recharge has been eliminated (or at least severely restricted) by the presence of 1,500 feet (450 meters) of permafrost in the Kuparuk Field area (Figure 1.4. Permafrost on the North Slope probably did not exist before the beginning of the Pleistocene Epoch (approximately 1.65 Ma; Collett, 1993a). The abundance of gasoline-range hydrocarbons increases with reservoir depth in West Sak 8I and 1-01 oils (Figures 2.8, 2.9; Table 2.3), but paraffins heavier than dodecane (n-C12) are not present in significant concentrations even in the deepest reservoir horizons. This suggests that these West Sak oils were subjected to an initial biodegradation event that removed all paraffins, isoprenoids, and light aromatic compounds, followed by a second charge of gas and condensate that varies in concentration with present reservoir depth. A similar model of initial biodegradation and secondary charge of light oil/condensate has been proposed for the Schrader Bluff (West Sak and Ugnu) oil accumulation at Milne Point northeast of the Kuparuk Field (Figure 1.1; Smalley et al., 1996). If this model is correct, why does the secondary charge

38 decrease from the deepest West Sak reservoir interval (zone A) to the shallowest reservoir interval (zone D; Figure 2.8)? If the shallowest zone simply received less secondary charge, then the isotopic compositions of the C6 and C7 compounds would be expected to be the same in all zones. The carbon isotopic compositions and concentrations of selected C6 and C7 hydrocarbons in West Sak oils are shown on Figures 2.10a and b. The deepest oils (tested from zone A) in the WSP 8I and WS 1-01 wells are isotopically lightest, and the B and D zone oils are shifted towards heavier isotopic compositions by up to 3. The isotopic compositions in the zone A oils are nearly identical in the WS 1-01 and WSP 8I wells, but the compositions in zones B and D differ (Figures 2.10, 2.11). In both wells, the concentration of the C6 and C7 hydrocarbons systematically decreases from the deepest to the shallowest reservoir zone (Figure 2.9). The variable isotopic compositions of C6 and C7 hydrocarbons that are observed in West Sak oils indicate that the decrease in secondary charge in zones B and D relative to zone A is not simply caused by less charge reaching the shallower zones. Some other processes capable of altering both the isotopic composition and concentration of the C6 and C7 hydrocarbons must be invoked to account for the observations. I believe that biodegradation is the process that best fits the geochemical data, although water washing, evaporative fractionation, geochromatography, and variations in source facies and/or maturity are other alternative hypotheses that are also considered below. The selective removal of hydrocarbon compounds by bacteria during biodegradation occurs roughly in the following sequence: n-alkanes, isoprenoid alkanes, low-ring cycloalkanes, and aromatics, although there is overlap and the relative resistance to biodegradation probably depends upon the environmental conditions (Rubinstein et al., 1977; Stahl, 1980; Tissot and Welte, 1984). The C6 and C7 compounds in West Sak oil exhibit systematic changes in concentration and isotopic composition that are consistent with a model of increased biodegradation in zones B and D relative to zone A (Figures 2.9, 2.10). All compounds decrease in concentration upwards and are shifted to heavier isotopic compositions, consistent with increased biodegradation and an associated kinetic isotope shift due to preferential removal of 12C in the shallower reservoir zones. Heptane decreases in average concentration by 80% between zones A and D, and exhibits an average isotopic shift of more than 3. The cycloalkanes methylcyclopentane, methylcyclohexane, and cyclohexane all have higher average initial concentrations in the zone A oils than heptane and experience roughly similar 80 to 88% decreases in concentration (Figure 2.9), but exhibit lower average isotopic shifts of 1.9 to 2.9. If it is assumed that heptane and the cycloalkanes are subjected to similar kinetic isotopic fractionation during biodegradation, the larger isotopic shift observed for heptane between zones A and D could indicate that it is more easily biodegraded than the cycloalkanes. However, 3methylhexane exhibits a relatively large average isotopic shift of 2.8 but only decreases in concentration by 50% from zone A to zone D. This relatively large isotopic shift that accompanies a smaller decrease in concentration suggests the possibility that 3-methylhexane is more highly fractionated during biodegradation than the other compounds. Although isoprenoids are more resistant to biodegradation than n-alkanes, pristine can be rapidly biodegraded by methanogenic microbes under some anaerobic conditions (Grossi et al., 2000). The removal of

39 methylcyclohexane during biodegradation appears to coincide with removal of isoprenoids in some oils (Alexander et al., 1983b). The aromatic compounds toluene and benzene exhibit only a 1 average isotopic shift and a decrease in concentration of only 27% (benzene) and 54% (toluene) between zones A and D. The fact that benzene and toluene exhibit the least change in concentration and isotopic composition is consistent with biodegradation but not with water washing. Experimental results have shown that under some anaerobic conditions alkylated aromatic compounds like toluene are more easily biodegraded than benzene, consistent with their behavior in West Sak oils (Wilkes et al., 2000). In contrast, benzene is the most soluble gasoline-range compound in crude oil and has been observed to be removed more rapidly than toluene during water washing (Connan, 1984; Palmer, 1993; Lafargue and Thiez, 1996). If water washing affected the West Sak oils, benzene should have exhibited the most change in concentration instead of the least change. The apparent lack of water-washing exhibited by C6 and C7 compounds may be attributable to migration of the secondary gas/condensate charge into the previously biodegraded West Sak oil, which would limit the contact between the gas/condensate charge and water. The preferential removal of toluene relative to benzene in West Sak oils may indicate that biodegradation occurred under anaerobic conditions. Under aerobic conditions, benzene is reported to be oxidized and removed more rapidly than toluene (Volkman et al., 1984). The concentrations of 1- and 2-methylnaphthalene decrease about 50% from zone A to zone D in 8I and 1-01 West Sak oils, similar to the 54% decrease in toluene concentration (Figure 2.9, Table 2.3). Smalley et al. (1996) related the 1- and 2-methylnaphthalene concentration in oils and cores at the Milne Point Field to the amount of secondary gas/condensate charge that was added to previously biodegraded oils. The isotopic compositions of the methylnaphthalenes were not measured in the West Sak 8I and 1-01 oils, but the fact that their concentration behaves similarly to toluene suggests that the decrease in concentration of 1- and 2-methylnaphthalene in the shallow West Sak oils may also be caused by biodegradation. If water washing caused the decrease in West Sak methylnaphthalene concentrations, then toluene should decrease in concentration more than the methylnaphthalenes, because toluene is much more soluble in water (Volkman et al., 1984). The 1- and 2-methylnapthalenes have been reported to be more rapidly biodegraded in oils than other alkylnaphthalenes (Rubinstein et al., 1977; Volkman et al., 1984; Williams et al., 1986). Increased biodegradation of West Sak oils in zones B and D relative to zone A is geologically reasonable. West Sak B and D zone sandstones were deposited in shallow marine or delta front environments that are more laterally continuous, more permeable, and closer to the surface than the inner shelf environments of zone A (Werner, 1987). West Sak oils in zones B and D would therefore likely have been subjected to more meteoric water recharge and biodegradation than the deeper zone A sandstones. Permeabilities in zone B sandstones are usually higher than in zone D sandstones, as observed in core from the WS 1-01 well (Figure 2.12). The average zone B core permeability is about three times higher than the average zone D core permeability in the 1-01 well. The higher zone B permeabilities would be expected to result in more fresh water recharge during aerobic biodegradation and/or faster delivery of reactants during anaerobic biodegradation, which may explain why most of the zone B C6 and C7 compounds are isotopically heavier than in zone D in the WS 1-01 well. The oil tested from zones B/A4 in the

40 WSP 8I well is a mixture that likely includes relatively pristine, unbiodegraded condensate-range compounds from zone A, which could explain why some compounds in zone B/A4 oil are isotopically intermediate between zone A oil in WSP 8I and zone B oil in WS 1-01 (Figure 2.11). I believe that changes in source rock maturity are not likely explanations for the changes in isotopic composition and concentration of C6 and C7 hydrocarbons in West Sak oils. Condensate-range maturity parameters such as the Heptane and Isoheptane Values defined by Thompson (1983) are relatively constant in West Sak oils and do not suggest any maturity differences between them (Table 2.4). Biomarker maturity parameters in the West Sak oils are also nearly identical in all three zones and provide no evidence for enough change in source rock maturity to produce the observed 1 to 3 isotopic shift in C6 and C7 compounds. The slight increase in the C29 ? ? ? -sterane 20S/20R ratio that is observed in the shallowest West Sak reservoir can be explained by moderate to heavy biodegradation, because the 20R epimer appears to be selectively removed during biodegradation (Alexander et al., 1983b; Volkman et al., 1984; Peters and Moldowan, 1993; Table 1.3). Increased biodegradation in zone D is also suggested by the increase in the C29 17? ,25-norhopane/C30 17? -hopane ratio observed between zones A and D, but the MPI maturity parameter remains relatively constant in all three zones (Table 1.3), presumably because alkylphenanthrenes are not easily biodegraded (Volkman et al., 1984). Isotopic variations caused by changing level of maturity during generation within a single oil family are usually less than 2 (Chung et al., 1998). Larger isotopic changes of up to 4 in n-alkanes and branched hydrocarbons were produced during artificial maturation of the asphaltene fraction from a North Sea oil, but no changes in methylcyclopentane, methylcyclohexane, or toluene isotopic composition were observed to occur with increasing pyrolysis temperatures (Rooney et al., 1998). Variations in source facies or proportions also cannot explain the isotopic differences between West Sak oils, in my opinion. Biomarker parameters indicative of source rock facies such as the C23 tricyclic terpane/C30 hopane and NDR ratios are relatively invariant between West Sak zones A and D (Table 1.3), indicating no significant change in Shublik source rock facies or proportions of Shublik and HRZ co-source. Any dilution of the Shublik charge by HRZ or Kingak-sourced oil in individual zones would have lowered their tricyclic terpane/hopane ratio (Tables 1.2, 1.3, and Figure 2.5). Moreover, it is difficult to conceive how any significant source rock variations could exist in the different West Sak oils, because the multi-billion barrel West Sak oil accumulation would have been previously homogenized by mixing in the original Prudhoe Bay trap and by remigration into the West Sak Field. Evaporative fractionation is another process that could have affected West Sak oils. Thompson (1987) defined evaporative fractionation as the complex of phenomena involved in the separation of gas from oil in the subsurface. Successive evaporative fractionations of a migrating gas/condensate charge from zone A up to zones B and D would result in lower concentrations of C6 and C7 compounds in the shallower zones, as observed in West Sak oils (Figure 2.9; Thompson, 1987). The relatively low paraffinicity observed in West Sak oils (Heptane Values < 11; Table 2.4) could be due to evaporative fractionation or to biodegradation, both of which can result in lowered Heptane and Isoheptane Values (Thompson, 1983, 1987). The changes in carbon isotopic composition of individual condensate-range compounds that

41 have been measured during evaporative fractionation are small (generally < 1; Carpentier et al., 1996) and therefore are not likely to account for the up to 3 isotopic shifts observed in C6 and C7 compounds in West Sak oils. In addition, compounds in the evaporatively fractionated vapor phase are isotopically lighter than in the residual oil (Carpentier et al., 1996; Dzou and Hughes 1993), so the isotopic composition of C6 and C7 compounds would be expected to become lighter upwards in response to repeated separation and migration of a vapor phase to the shallowest West Sak reservoirs. West Sak oils do not conform to the isotopic trend predicted by evaporative fractionation, because the C6 and C7 compounds are isotopically heaviest in the shallower B and D zones. It is possible, however, that the isotopic fractionation caused by biodegradation has obscured any small isotopic changes caused by evaporative fractionation in West Sak oils. Migration through the West Sak interval could potentially alter the composition of the secondary gas/condensate charge through geochromatographic interactions between the water/rock system and the migrating hydrocarbons. Most isotopic or molecular fractionations caused by geochromatography should decrease or disappear, however, after passage of the concentration front of migrating hydrocarbons (Fuex, 1980; Krooss et al., 1991). The isotopic composition of natural gas and oil is thought to be relatively unaffected (< 1 fractionation) by migration over short distances (Stahl, 1977; Fuex, 1980). There are some conflicting viewpoints in favor of larger fractionations during migration (Prinzhofer et al., 1995; Prinzhofer and Pernaton, 1997), although the time periods assumed for these postulated fractionations are sometimes short (e. g. 104 years) and the fractionation may disappear as migration continues over geologic time scales (Fuex, 1980; Prinzhofer et al., 2000). It is postulated in this chapter that a small (~ 0.8) isotopic fractionation occurred during the evaporative fractionation of a vapor phase from the Kuparuk Field oil accumulation, and that this gas/condensate charge migrated up to the West Sak zone A reservoir where it was added to a previously biodegraded oil. The small isotopic fractionation that I infer between C6 and C7 compounds in Kuparuk and West Sak oils is similar in magnitude to the fractionation measured in evaporative fractionation experiments (Carpentier et al., 1996). In order for this small isotopic fractionation to be preserved in West Sak zone A oils, the gas/condensate charge could not have been significantly altered by additional isotopic fractionation during migration between or within the Kuparuk and West Sak reservoirs. If migration of the gas/condensate charge between the Kuparuk and West Sak Fields occurs along faults planes that connect the two reservoirs, as hypothesized in this chapter, then geochromatographic contact with the pore system would be minimal compared with migration through the mudstone seal separating the two reservoirs. In summary, I believe that biodegradation is the best explanation for the changes in concentration and isotopic composition observed in West Sak C6 and C7 compounds. Biodegradation of the condensate-range compounds is also consistent with independent evidence for biodegradation of West Sak solution gas. Benzene and toluene experience the least isotopic shift and least decrease in concentration in the shallow West Sak reservoir zones and therefore appear to be more resistant to biodegradation than heptane, 3-methylhexane, and the cycloalkanes in West Sak oils. The hydrogen isotopic composition of methane in West Sak gases suggests that at least some of the biodegradation of West Sak hydrocarbons took place under anaerobic conditions, and the relative resistance of individual compounds to biodegradation might differ in other environmental conditions.

42 I infer that the original moderate to heavy biodegradation of West Sak oils occurred under aerobic conditions because of the observed increase in biodegradation updip that is coincident with a decrease in salinity indicative of meteoric water flushing (Werner, 1987). This original biodegradation event is postulated to have removed all the n-alkanes, isoprenoids, and light cycloalkane and aromatic compounds from West Sak oil, and altered the 25-norhopane/hopane and C29 sterane 20S/20R biomarker ratios. In the model presented in this chapter, the original biodegradation event was followed by migration of a secondary gas/condensate charge that was then lightly biodegraded in the shallowest West Sak reservoirs. Because this postulated secondary gas/condensate charge would have accumulated in the previously biodegraded West Sak oil pool, contact with meteoric water and water washing may have been limited, and biodegradation could have occurred in an anaerobic environment. The interpreted increase in biodegradation of the gas/condensate charge in West Sak zones B and D relative to zone A could then be attributed to greater reservoir permeability, connectivity, and faster delivery of reactants to the microbial population under anaerobic conditions. Alternatively, the West Sak zone B oils may be in closer proximity to an oil-water contact that provided oxygen for initial aerobic biodegradation of the gas/condensate charge, and the biogenic West Sak methane may have been generated subsequently under anaerobic conditions. Development wells drilled in the West Sak Field have encountered shallower oil-water contacts in the B zone than in the A and D reservoir zones (M. Werner, oral comm. 2000). SOURCE OF WEST SAK LIGHT HYDROCARBONS The carbon isotopic compositions of the C6 and C7 compounds from zone A in the West Sak 8I and 1-01 wells are virtually identical and indicate a common origin for these gasoline-range compounds prior to their alteration in the shallower B and D zones (Figure 2.11). The two most likely candidates for the source of the West Sak condensate-range compounds are continued leakage from the Prudhoe Ivishak oil accumulation (which is the postulated source of the original biodegraded West Sak oil), or leakage of a gas/condensate charge from the Kuparuk reservoir that underlies the West Sak Field. The C6 and C7 compounds in West Sak zone A oils fall in the same isotopic range and closely match the isotopic pattern of the underlying Kuparuk Field oils (Figure 2.13a). The relatively high concentrations of methylcyclopentane, cyclohexane, and methylcyclohexane in the West Sak zone A oils also mirror their high concentrations in Kuparuk oils (Figure 2.9). The best matches to West Sak zone A isotopic compositions are the 1D-04 Kuparuk Field oil, which directly underlies the West Sak oils, and the two nearest Kuparuk reservoir oils from the 1E-11 and W Kuparuk 3-11-11 wells. The West Sak zone A C6 and C7 compounds are consistently isotopically lighter than the 1D-04 and 1E-11 oils by up to 1.2, and on average the Kuparuk C6 and C7 compounds in the 1D-04 well are about 0.6 heavier than in the West Sak zone A oils. The isotopic match is not as good with the more distant 2W-12 Kuparuk oils, but is still much better than with the Prudhoe Bay Field oils discussed below. In my opinion, the excellent isotopic correlation between C6 and C7 compounds in West Sak zone A oils and Kuparuk Field oils indicates that the secondary gas/condensate charge in the West Sak Field was derived from the underlying Kuparuk Field oils.

43 The isotopic compositions of C6 and C7 compounds in the Ivishak reservoir at the Prudhoe Bay Field are not a good match with the West Sak oils. The West Kuparuk 3-11-11 well is located about 5 miles (8 kilometers) east of the West Sak 8I and 1-01 wells, and the 4-05 and 17-01 wells are located approximately 20 miles (32 kilometers) east (Figure 2.1). Note that in all three Prudhoe Ivishak oils, toluene is isotopically heavier (i. e. less negative) than methylcyclohexane, and benzene is heavier than cyclohexane and methylcyclopentane, while the reverse is true for the West Sak oils (Figure 2.13b). The only Prudhoe Field area oil that matches the West Sak C6 and C7 isotopic pattern is the oil tested from the Kuparuk reservoir at the West Kuparuk 3-11-11 well immediately east of the Kuparuk River Field (Figure 2.13a). The C6 and C7 isotopic differences between oils tested from the Kuparuk and Ivishak reservoirs in the 3-11-11 well provide further evidence against Carman and Hardwicks (1983) suggestion that the Ivishak oil spilled up the Eileen fault into the Kuparuk reservoir. The C6 and C7 compounds in the Prudhoe 4-05 well are 1.7 to 3.7 heavier than in the other two Prudhoe Ivishak oils. The 1 to 3 isotopic shift observed in shallow West Sak oils is similar in magnitude and is interpreted as evidence for biodegradation of West Sak oils, as previously discussed. The distribution of biomarkers and isotopically heavy compounds in Prudhoe Bay 405 oil differs in several important aspects from zones B and D at West Sak Field, however, and I believe that a process other than biodegradation accounts for the isotopically heavy composition of C6 and C7 compounds in the 4-05 oil. In the Prudhoe Bay Ivishak oils, toluene, heptane, and cyclohexane are all about 2 heavier in the 4-05 oil relative to the 3-11-11 and 17-01 oils. This is difficult to explain by the process of biodegradation, because toluene would be expected to be more resistant to biodegradation than the alkanes and cycloalkanes, and would be expected to exhibit a lower isotopic shift as is observed in the West Sak oils. In addition, the C29 25norhopane/C30 hopane ratio is identical in the 4-05 and 17-01 oils (Table 1.3), so I believe that biodegradation is not likely to be the cause of the heavier 4-05 isotopic composition. The relatively heavy 4-05 isotopic composition is probably due to a higher proportion of HRZsourced oil. The 24-nordiacholestane concentration in 4-05 Ivishak oil is higher than in W Kuparuk 3-11-11 and 17-01 Ivishak oils (NDR ratio, Table 1.3), indicating higher HRZ input to the 4-05 oil. In contrast, the NDR ratios in West Sak zone B oils are less than or equal to NDR ratios in zone A, so increased HRZ co-source proportions cannot account for the heavier isotopic compositions observed in West Sak oils. Kerogen pyrolyzate from HRZ source rock is about 1 heavier than pyrolyzate from Shublik and Kingak source rocks (Sedivy et al., 1987). The distillate fraction of Endicott Field oil, which has a large HRZ source component (Wicks et al., 1991), is about 2 heavier than the distillate fraction of Kuparuk Field oils (Sedivy et al., 1987). The DS 4-05 well is located in the northeastern part of the Prudhoe Bay Field where the HRZ shale directly overlies the Ivishak reservoir along the Lower Cretaceous Unconformity (Figure 2.2). The Kekiktuk reservoir at the Endicott Field in the Duck Island Unit immediately east of Prudhoe Bay (Figure 2.1) is also unconformably overlain by HRZ source rock. The 4-05 oil was tested from the lower part of the Ivishak reservoir that is compartmentalized by prodelta and floodplain shales (Tye et al., 1999), which may explain why its unique C6 and C7 isotopic composition was not homogenized by mixing in the high-permeability Ivishak reservoir. Another alternative explanation for the heavier isotopic composition of the C6 and C7 compounds in DS 4-05 oil is that the oil could have been generated at a higher maturity than the

44 other two Ivishak oils. This alternative is considered unlikely because the C29 sterane 20S/20R and MPI biomarker ratios indicate no significant maturity differences between the 4-05, 17-01, and W Kuparuk 3-11-11 Ivishak oils (Table 1.3). The Heptane and Isoheptane maturity parameters defined by Thompson (1979, 1983) also indicate no significant maturity differences in condensate-range compounds between the three Ivishak oils (Table 2.4). LOSS OF LIGHT HYDROCARBONS FROM KUPARUK OILS BY EVAPORATIVE FRACTIONATION All Kuparuk Field oils show evidence of light hydrocarbon loss by evaporative fractionation (Figure 2.14, Table 2.5), a process described by Thompson (1987). Thompson performed a series of experiments in which the gas phase of a gas-saturated oil was allowed to escape from the oil. He noted that some compounds such as toluene and cycloalkanes were relatively enriched in the residual oil, while other compounds such as heptane were preferentially dissolved in the gas phase that escaped. Thompson showed that ratios of toluene/heptane and methylcyclohexane/heptane increase systematically in residual oils with increasing light hydrocarbon loss. Oils from the present-day structural crest of the Kuparuk Field (Group 1) possess the highest toluene/heptane ratios and lowest heptane/ methylcyclohexane ratios, and therefore experienced the most light hydrocarbon loss when measured by these Thompson parameters (Figure 2.14). This trend is opposite to the trend predicted by gravity segregation. In a gravity-segregated oil column, the highest concentration of aromatic compounds such as toluene should be at the base of the oil column (Schulte, 1980). The oils at the crest of the Kuparuk structure probably had higher initial saturations of solution gas, and therefore would lose more gas than the deeper Group 2 oils during evaporative fractionation. At field discovery, solution gas-oil ratios (GORs) in Group 1 oils at the crest of the field were about 550 standard cubic feet of gas per stock tank barrel (SCF/STB), versus 350 SCF/STB in the Group 2 oils 1000 feet deeper at the base of the oil column. If leakage of solution gas from the Kuparuk Field to the overlying West Sak reservoir occurred as hypothesized in this chapter, then the volume of gas/condensate lost from the Kuparuk Field by evaporative fractionation should be approximately equivalent to the volume of secondary gas/condensate charge in the overlying West Sak reservoir. It is difficult to estimate the amount of gas/condensate lost from Kuparuk Field, however, because all of the Kuparuk Field oils are interpreted to have experienced evaporative fractionation and the composition of pristine Kuparuk Field oil prior to loss of light hydrocarbons must be assumed in the calculation. If it is assumed that pristine Kuparuk Field oils were similar in composition to present-day Prudhoe Bay Field oils, then a simple light hydrocarbon mass balance calculation can be performed on the C15- fraction of the West Sak and Kuparuk Field oils. The C15- fraction of the oil is approximated by its topping loss in the mass balance calculation. Topping loss is defined as the weight percent of oil that is lost when it is placed under a stream of nitrogen at 400C for one hour. West Sak oils from zone A have higher topping losses than oils from zones B and D because the oils from zone A have more of the secondary gas/condensate charge (Figure 2.8). In the light hydrocarbon mass balance calculation, it is assumed that West Sak light hydrocarbon content is approximated by the topping losses of 11 to 23 weight per cent observed in West Sak oils in the current development area (Table 2.1). Kuparuk light hydrocarbon loss is approximated

45 by the difference between a typical Prudhoe oil topping loss (33%) and the average topping loss in 23 analyzed Kuparuk oils (16%), for an average Kuparuk light end loss of 17 weight per cent (Tables 2.1, 2.5). With these assumptions and with oil volumes and densities taken from a one square kilometer area at 1E Pad in the West Sak and Kuparuk Fields, the mass of Kuparuk light hydrocarbons lost is estimated to be 400,000 metric tons. In comparison, the mass of light hydrocarbons present over the same area in the overlying West Sak reservoir is estimated to range from 200,000 metric tons to 1.2 million metric tons, depending upon which West Sak topping loss and oil column thickness is assumed in the calculation. Any gas and condensate that leaked from the Kuparuk Field would be expected to migrate and become concentrated in individual West Sak accumulations after it reached the West Sak reservoir, so it is possible that the volume of light hydrocarbons trapped in the West Sak interval could be larger than the Kuparuk losses in a small area. It is not possible to perform the mass balance calculation over the entire area of the West Sak Field, because the West Sak oil volume and light hydrocarbon content outside of the current development area are not known. The approximate equivalence of the light hydrocarbons lost from the Kuparuk reservoir and the light hydrocarbons present in the current West Sak development area indicates that evaporative fractionation and leakage is a viable hypothesis. An external source of methane is frequently invoked to strip the residual oil during evaporative fractionation (Thompson, 1987; Meulbroek et al., 1998). Oils that have been stripped with excess methane, or gas-washed, can be identified by depleted light alkanes on a plot of molar alkane concentration versus carbon number. The Kuparuk 1E-11 oil shown on Figure 2.15 is slightly depleted in n-C8 n-C10 alkanes relative to the 4-05 Prudhoe Bay Ivishak oil, but does not exhibit the high degree of depletion that results from stripping by large quantities of excess methane. Evaporative fractionation of Kuparuk oil therefore appears to have resulted from loss of solution gas or loss of a paleo-gas cap rather than from gas washing. ISOTOPIC EVIDENCE FOR EVAPORATIVE FRACTIONATION OF KUPARUK OILS Carpentier et al. (1996) recently demonstrated an isotopic enrichment of 12C in condensaterange compounds in the gas phase relative to the residual oil during an evaporative fractionation experiment conducted at 1340C with a pressure drop from 335 bar to 240 bar (33,500 kilopascals to 24,000 kilopascals). Carpentier et al. (1996) were not able to directly measure the isotopic fractionations of the C6 and C7 compounds because of evaporative fractionation during heating of their stored condensate from 760C to room temperature that affected their experimental results at low carbon numbers. The isotopic fractionation factors that Carpentier et al. (1996) measured for n-C9 n-C13 during a single evaporative fractionation corresponded to a 12C enrichment of 1 or less in the evaporated condensate-range compounds relative to the original oil. The C6 and C7 compounds in the West Sak zone A oils are isotopically lighter than the same compounds in the underlying Kuparuk 1D-04 residual oil by 0.6 on average, consistent with an origin by evaporative fractionation (Table 2.2; Figure 2.13a). Similar small isotopic enrichments of 13C in residual, evaporatively fractionated oils have been reported by Dzou and Hughes (1993) and by Curiale and Bromley (1996). The 0.6 average isotopic difference compares with an average standard deviation of 0.24 for triplicate analyses of all of the oils in

46 this study and an average difference of 0.2 for compounds present at greater than 0.1% concentration in replicate samples (Tables 2.2, 2.3). Using the Students t distribution and the standard deviations calculated from triplicate analyses (Table 2.2), there is at least an 80% probability that the mean isotopic compositions of benzene, cyclohexane, 3-methylhexane, and heptane differ between the Kuparuk 1D-04 oil and the West Sak 1-01 zone A oil (Davis, 1986). For cyclohexane and heptane, the probability is greater than 95% that the mean isotopic compositions in the two oils differ. The mean isotopic compositions of methylcyclopentane, methylcyclohexane, and toluene differ by 0.3 or less in the 1D-04 and 1-01 oils and can be considered indistinguishable within experimental error. If it is assumed that the migrant gas/condensate in zone A of the WS 1-01 well was evaporatively fractionated from the underlying Kuparuk reservoir in the vicinity of the 1D-04 well, it is possible to calculate the isotopic fractionation ? between the vapor and liquid phases that separated in the Kuparuk reservoir. It is assumed in the calculation that no further isotopic fractionation occurred during migration between the Kuparuk and West Sak zone A reservoirs, and that the isotopic differences between methylcyclopentane, methylcyclohexane, and toluene in the 1-01 and 1D-04 oils fall within experimental error and are therefore excluded from the calculation. With these assumptions, an average isotopic fractionation factor ? ? gas/liquid) of 0.99919 is calculated between the West Sak 1-01 zone A migrated gas/condensate and the Kuparuk 1D-04 residual oil (Table 2.6). This inferred fractionation factor equates to an average isotopic difference of 0.8 and falls within the 0.99911 to 0.99936 range of fractionation factors for n-C9 n-C13 measured in the evaporative fractionation experiment of Carpentier et al. (1996). Whiticar and Snowdon (1999) report similar small (0.5 1.0 maximum) isotopic enrichments of individual compounds in residual oils that have been evaporatively fractionated due to poor sample storage in the lab. The C6 and C7 compounds in Kuparuk 2W-12 oils that have experienced lower evaporative fractionation, as measured by Thompson parameters (Figure 2.14), are isotopically lighter by 0.6 on average than the 1E-11 and 1D-04 oils that have experienced more evaporative fractionation (Figure 2.13a). The isotopic compositions in Kuparuk 1D-04 and 1E-11 oils differ from each other by only 0.1 on average, and most of their C6 and C7 compounds are isotopically indistinguishable within experimental error. The heavier isotopic compositions of the 1E-11 and 1D-04 Kuparuk oils that have been subjected to more evaporative fractionation than the 2W-12 oils provide further evidence in support of the evaporative fractionation hypothesis and for the small isotopic fractionation that I interpret in this study. The heavier isotopic composition of 1E-11 and 1D-04 C6 and C7 compounds likely resulted from more loss of gas than the 2W-12 oils during single or multiple episodes of evaporative fractionation. The 1E-11 well is located in an area with a higher density of faults connecting the West Sak and Kuparuk reservoirs than in the 2W-12 area (Dzou and Masterson, written comm. 1993). The isotopic differences between Kuparuk and West Sak zone A condensate-range compounds are not likely to be caused by biodegradation, because the West Sak zone A oils display no evidence for biodegradation in the C6 to C7 range, with the possible exception of heptane discussed below. Even if the C6 and C7 compounds in West Sak zone A oils were slightly altered due to incipient biodegradation, they would be heavier, not lighter, than in Kuparuk oils due to the kinetic isotope shift produced during biodegradation.

47 The relative changes in C6 and C7 compound concentrations between Kuparuk oil and West Sak zone A oils are consistent with an origin by evaporative fractionation, with the exception of heptane (Figure 2.9). The cycloalkanes increase in concentration relative to toluene and benzene in the migrant West Sak zone A condensate, as predicted during evaporative fractionation (Thompson, 1987; Carpentier et al., 1996). However, the heptane concentration in West Sak zone A oils should be higher relative to the cycloalkanes, because heptane is more strongly partitioned into the gas phase than the cycloalkanes during evaporative fractionation. The unexpectedly low concentration of heptane in West Sak zone A oils could be caused by preferential biodegradation and removal of heptane even in the deepest West Sak oils that otherwise display no evidence for biodegradation in their condensate range. The condensaterange compound concentrations analyzed in this study (with the exception of heptane) in West Sak zone A oils are similar to unaltered Kuparuk oils, and the West Sak zone A oil gravities are almost as high as Kuparuk oil gravities (Tables 2.1, 2.3). Shallower West Sak oils from zones B and D exhibit reduced concentrations in all the C6 and C7 compounds and have lower API gravities due to biodegradation, as previously discussed. If incipient biodegradation has indeed preferentially altered the concentration and isotopic composition of heptane in West Sak zone A oils, then the isotopic fractionation factor ? ? gas/liquid) inferred for heptane (Table 2.6) is in error. Incipient biodegradation of heptane in zone A would also complicate the determination of resistance to biodegradation that is inferred from changes in concentration between zones A, B, and D. MECHANISM FOR GAS LEAKAGE FROM KUPARUK FIELD Any gas and condensate that leaked from the Kuparuk Field would have to migrate 3,000 feet (910 meters) vertically through the HRZ Formation and the Colville Group mudstones in order to reach the West Sak reservoirs (Figure 2.2). The HRZ Formation is an organic-rich mudstone that averages 150 feet (45 meters) in thickness over the entire Kuparuk Field area and forms an excellent seal for both the Kuparuk and Prudhoe Bay Fields. Mercury injection capillary pressure measurements performed on HRZ core samples indicate that an oil column height of more than 3,500 feet (1,100 meters) would be required to cause failure of the seal. Because the Shublik source rock is buried only 2,200 feet (670 meters) below the Kuparuk reservoir and the Kuparuk oils were generated at relatively low maturities and gas-oil ratios, it is unlikely that paleohydrocarbon column heights could have been sufficient to cause leakage through the HRZ seal. A more likely mechanism for gas leakage is provided by north/northeast-striking faults that displace the Kuparuk reservoir (Figures 2.1, 2.2). Several north/northeast-striking faults connect the Kuparuk and West Sak reservoirs in the vicinity of the WS 1-01 and WSP 8I wells. Faults that dip to the east outnumber faults that dip to the west by a ratio of 5:1, which is compatible with their formation during eastward tilting and uplift contemporaneous with Paleogene thrusting and associated crustal loading 50 miles (80 kilometers) east in the Arctic National Wildlife Refuge (Bird, 1985; Masterson and Paris, 1987; Figure 1.1). At least three episodes of Paleogene thrusting and associated crustal uplift have been identified in the ANWR from fission track measurements (OSullivan et al., 1993), and it is possible that successive thrusting episodes may have reactivated east-dipping faults that allowed gas and condensate to escape upwards from the Kuparuk Field into the West Sak Field.

48 The faults that connect the West Sak and Kuparuk reservoirs appear to be closed to oil or gas migration at present. If oil from the Kuparuk Field was leaking up the faults today, paraffins heavier than the gas/condensate range would be present in the deepest and least biodegraded West Sak zone A oils (Figure 2.8). The biomarker signature of West Sak oil is very similar to Prudhoe Bay Field oil (Figure 2.5), suggesting that leakage of Kuparuk gas/condensate was not accompanied by significant leakage of Kuparuk Field oil. Gas migration is not possible at present because the Kuparuk oil is undersaturated with gas, and the Kuparuk reservoir pressure would have to drop about 200 psi (1,380 kilopascals) before gas could come out of solution and migrate up faults. Since all oils in the Kuparuk reservoir show evidence of evaporative fractionation (Figure 2.14), the gas must have separated from the oil in the Kuparuk reservoir before migrating up to the West Sak interval. The present-day pressure gradient between the Kuparuk and West Sak reservoirs is about 0.67 psi/ft (15 kilopascals/meter). If the Kuparuk and West Sak reservoirs were in hydrostatic pressure communication along faults today at an average seawater pressure gradient of 0.465 psi/ft (10.5 kilopascals/meter), the Kuparuk reservoir pressure would drop approximately 500 psi (3,450 kilopascals), allowing gas to come out of solution and migrate up the faults. If the Kuparuk Field oil was fully gas-saturated in Tertiary time when the north/northeast-striking faults broke through the shale separating the Kuparuk and West Sak intervals, any reduction of reservoir pressure would have allowed gas to come out of solution, and evaporative fractionation of the Kuparuk oil could occur. Burial history models by D. Masterson in the Kuparuk Field area suggest that about 1,500 feet (450 meters) of Tertiary uplift accompanied formation of the north/northeast-striking faults. Subsequent repressurization of the Kuparuk reservoir after uplift ceased would then be necessary to undersaturate the Kuparuk oil. About 430 feet (130 meters) of reburial would be needed to produce the present-day undersaturation of 200 psi (1,380 kilopascals). The presence of up to several hundred feet of Pliocene and Pleistocene sediments in the Kuparuk Field area provides support for the hypothesis that reburial created the present-day undersaturated Kuparuk oils, but the age and thickness of the sediments in the surficial permafrost zone are not well constrained. IMPLICATIONS FOR DEVELOPMENT OF WEST SAK OIL RESERVES The West Sak petroleum filling history model presented in this chapter predicts that oils with the highest API gravities will be trapped in the structurally deepest parts of the West Sak accumulation that have had the least exposure to biodegradation. Leakage from the Kuparuk accumulation provides the critical secondary gas/condensate charge that enhances the API gravity and viscosity of West Sak Field oils (Figure 2.8). Wells located south of the Kuparuk Field have thus far failed to encounter any West Sak oils with gravities and viscosities suitable for waterflooding, in accordance with the model presented in this chapter, because there is not a thick underlying Kuparuk oil column to provide a secondary gas/condensate charge. However, thin Kuparuk sandstones are present in some areas south of the field boundary, and may locally contribute a volumetrically limited gas/condensate secondary charge to overlying West Sak oils. Outside of the Kuparuk Field area, a secondary gas/condensate charge to biodegraded West Sak oils could also be provided by different underlying reservoirs, or by continued leakage from the Prudhoe Bay Field or other accumulations.

49 CONCLUSIONS 1. Oil from the Prudhoe Bay Field spilled and migrated 10 miles (16 kilometers) laterally and 5,000 feet (1,525 meters) vertically into the shallow West Sak Field, where it was trapped and moderately biodegraded. 2. Gas and condensate leaked 3,000 feet (910 meters) vertically from the underlying Kuparuk Field, adding a secondary condensate charge to the previously biodegraded oil in the West Sak Field. The secondary gas/condensate charge then appears to have been lightly biodegraded in the shallowest West Sak reservoirs, possibly under anaerobic conditions, producing a kinetic isotopic shift to heavier carbon isotopic ratios by up to 3. Benzene and toluene experience the least isotopic shift and least decrease in concentration in the shallow West Sak reservoir zones and therefore appear to be more resistant to biodegradation than heptane, 3-methylhexane, and the cycloalkanes. 3. All Kuparuk Field oils show evidence for light hydrocarbon loss by evaporative fractionation. A slight carbon isotope fractionation (~ 0.8) in C6 and C7 compounds is inferred between Kuparuk oil and migrant gas/condensate in the West Sak zone A oils, similar to the isotopic fractionation measured in the evaporative fractionation experiments of Carpentier et al. (1996). The Kuparuk oils that have experienced the most evaporative fractionation also exhibit the most enrichment of 13C, consistent with the interpretation that the isotopic fractionation occurred during separation of a vapor phase within the Kuparuk reservoir, and not along the migration pathway to the West Sak Field. 4. West Sak oil gravities are predicted to be highest in the structurally deepest part of the accumulation in areas that overlie the Kuparuk accumulation. The model presented in this chapter predicts that oil in biodegraded West Sak reservoirs that have not received a secondary gas/condensate charge may be too viscous to develop by conventional waterflooding methods.

CHAPTER THREE BURIAL HISTORY MODELS INTRODUCTION The geologic setting and origins of oils and gases in the central Alaskan North Slope are discussed in Chapters 1 and 2. This chapter presents burial history reconstructions and discusses the modeled filling histories of the Prudhoe Bay, Kuparuk, West Sak, Pt. McIntyre, Alpine, and Tarn Fields. The modeling was accomplished with EXODUS, a proprietary map-based burial history model that was developed by Zhiyong He at ARCO. EXODUS is now being revised and marketed to the public; contact Dr. He at 1328 Newbury Lane, Plano, TX 75075 for information about its current availability. Although the EXODUS model is quite simple and executes on a desktop computer in seconds, it nevertheless provides a reasonable prediction of the bulk properties of a mixed Prudhoe Bay Field crude oil that was generated from three source rocks over a time span of more than 65 million years. Modeling also reveals insights into the filling histories of the other central North Slope fields and provides testable hypotheses for the origin and areal distribution of mixed oils and gases derived from more than one source rock. The burial history models of most of the individual wells used in this study were originally constructed with proprietary GENESIS software by Jeff Corrigan at ARCO. These models were modified extensively by the author to ensure consistency of the stratigraphic layers for the EXODUS model and were all re-calibrated against measured vitrinite reflectances to create a consistent isopach map of removed overburden in the study area. Custom kinetics for hydrocarbon generation from Shublik, Kingak, and HRZ source rocks were added to all the burial history models by the author. Erik Tegelaar (written comm. 1993) previously analyzed some of the source rock kinetics samples that were used in this study. All the research reported in Chapter 3 was done by the author, including construction of all EXODUS model layers, identification of oil and gas windows, interpretation of tectonic controls on faulting and vertical migration, and reconstruction of the burial and petroleum filling histories of all the fields. SYNOPSIS The petroleum generation, migration, and filling history of the central Alaskan North Slope was reconstructed with a simple map-based burial history model that was calibrated with source rock and oil geochemistry in the area surrounding the Prudhoe Bay, Kuparuk, West Sak, Pt. McIntyre, Tarn, and Alpine Fields. The oil charge to the Prudhoe Bay Field paleostructure and eastern Barrow Arch is modeled to have begun in Late Cretaceous time from Shublik and Kingak source rocks southwest of the field. At the close of Late Cretaceous time, the top of the Prudhoe Bay reservoir was within 2000 feet of the surface, and geochemical evidence suggests that the early oil charge to the field was biodegraded. Migration of gas and HRZ-sourced oil into the Prudhoe Bay field paleoclosure reached a peak in Middle Eocene time and continued to the present day. Generation of carbon dioxide gas from decarbonation of the Lisburne Formation peaked in Eocene time at maximum burial depth in the model.

50

51 Formation of the Prudhoe Bay Field tar mat likely began when a Paleogene gas charge arrived and began to deasphalt the accumulation, and continued as the oil-water contact swept upward through the reservoir during post-Eocene burial, tilting, and spillage. Tar mat formation may have been enhanced by thermal convection in the Prudhoe Bay oil column caused by the presentday 350C lateral temperature gradient in the field. Spillage of Prudhoe oil from the main field area into the West Sak Field occurred during postEocene uplift and eastward tilting that was probably caused by thrusting and crustal loading 50 miles southeast of the field in the Arctic National Wildlife Refuge. The 1 to 2 degree eastward tilt decreased the hydrocarbon column at Prudhoe Bay Field from 2400 to 1000 feet and created the structural trap at the Prudhoe Bay West End in the model. Tilting also caused formation of north/northeast-striking faults and reactivated older east and northwest-striking faults from the Lower Cretaceous rifting event. Oil likely spilled from the Prudhoe Bay Field to the West Sak reservoir along west and northwest-striking faults that were subparallel to the direction of tilting and inferred maximum horizontal stress. When the spilled oil reached the West Sak interval, it migrated updip to the West Sak Field. Kuparuk oils are modeled to migrate vertically into the Lower Cretaceous Kuparuk River Formation from underlying Shublik source rock when the Kuparuk Field structural closure began to form in Eocene time. The 6 billion barrels of oil in place at Kuparuk Field closely matches the estimated volume of 6 billion barrels expelled from Shublik source rock directly beneath the field. Vertical migration from underlying source kitchens along northwest-striking faults provides an explanation for the origin of mixed oils co-sourced from Shublik and Kingak sources rocks west of Kuparuk Field, and also provides a mechanism for Shublik-sourced gas to mix with Kingak and HRZ-sourced oil in Tarn and Alpine Fields. The total expelled oil volume within the Prudhoe Bay Field fetch area of 4,000 square miles is modeled to be 168 billion barrels and consists of 59% Shublik, 28% HRZ, and 13% Kingak source rock contribution. The estimated 40 to 50 billion barrels of original oil in place in the Prudhoe Bay and West Sak Fields imply a migration efficiency of 25 to 30% in the fetch area for the Prudhoe Bay Field. This relatively high migration efficiency likely reflects the fact that all three source rocks are in direct contact with the Ivishak and Sag River Sandstone reservoirs at the Prudhoe Bay Field, and that a Prudhoe paleo-trap with a large fetch area has existed since Late Cretaceous time. The carbon isotopic composition, API gravity, and sulfur content of the Prudhoe Bay main field oil accumulation closely match the modeled oil composition in the Prudhoe Bay fetch area. These results demonstrate that despite the many assumptions and simplifications inherent in the map-based model, it nevertheless provides a powerful tool to predict the filling histories of exploration prospects in complex petroleum systems. METHODS SOURCE ROCK ANALYSES The reaction kinetics for hydrocarbon generation from Shublik, Kingak, and HRZ source rocks were determined using an open system, non-isothermal Pyromat II micropyrolyzer. Samples were analyzed with multiple constant heating rates of 1, 5, 15, and 500C/minute from 2500C to 6500C. The Lawrence Livermore National Laboratory (LLNL) KINETICS program was used to

52 calculate kinetic parameters assuming first order reactions and using a single value for the preexponential frequency factor (A) and a distribution of discrete activation energies (E) with 1000 cal/mole spacing (Table 1; Braun and Burnham, 1994). A second Tmax-shift model, also known as the approximate Gaussian distribution model, was calculated for a Shublik and a Kingak sample to compare with the discrete activation energy distribution. Rock Eval analyses and vitrinite reflectance measurements were provided by Humble Instruments and Services, Inc. in Humble, TX and by DGSI in The Woodlands, TX. In source rocks where solid hydrocarbons were present, equivalent vitrinite reflectances were calculated from solid hydrocarbon reflectances using the correlation of Landis and Castao (1995). BURIAL HISTORY MODELS Burial history modeling was accomplished with GENESIS and EXODUS software developed by Zhiyong He and others at ARCO. GENESIS is a proprietary 1D basin modeling program that includes a steady-state heat conduction model and calculates source rock transformation rates from custom measurements of kerogen kinetics (Z. He, written comm. 1992). All modeled vitrinite reflectances reported in this study were calculated with the LLNL kinetic model (Burnham and Sweeney, 1989). Burial history models at 43 well locations were constructed with GENESIS to model the timing of hydrocarbon generation and the magnitude of Tertiary uplift associated with post-Eocene eastward tilting (Bird, 1985; Figure 3.1). Vitrinite reflectance and bottomhole temperature measurements in the wells were used to calibrate the amount of uplift and heat flow used in the models. The modeled sensitivities to heat flow and removed overburden thickness are illustrated with burial histories from the Phoenix #1 and Bush Federal #1 wells (Figures 3.2, 3.3). These burial histories were constructed with the GENESIS 1D modeling software package. In both models, the Carboniferous through Jurassic heating rate was less than 0.50C /my, and the Cretaceous through Tertiary heating rate was about 10C /my when most of the oil was generated during deposition of the Brookian Sequence. Two major episodes of uplift are modeled: the Lower Cretaceous Unconformity (LCU) along the Barrow Arch shown on the Phoenix model, and the post-Middle Eocene uplift shown in both models. Lisburne, Shublik, Kingak, and HRZ source rocks reach or pass through the oil window (> 1000C) into the gas window (> 1500C) in the Bush well at burial depths of up to 20,000 feet (6100 meters), but barely enter the oil window at burial depths of less than 12,000 feet (3650 meters) at the Phoenix well. The North Slope surface temperature is modeled to vary with time, with a maximum in Late Cretaceous time that was 200C warmer than the present-day mean annual temperature of about 100C. Dinosaurs inhabited the North Slope during Late Cretaceous time (Clemens and Nelms, 1993). Spicer (1987) used angiosperm floral data to estimate a North Slope mean annual temperature of 100C during Albian-Cenomanian time that decreased to 50C in Maastrichtian time. The effect of this modeled temporal temperature variation is that source rocks require less burial to reach the oil window in Late Cretaceous time than they do in Tertiary time, and a significant quantity of oil is therefore generated in Late Cretaceous time instead of early Tertiary time in the model. A heat flow of 1.3 Heat Flow Units (1.3 x 10-6 cal cm-2 sec-1) was used in all the modeled wells. The Phoenix #1 model shows the lack of agreement with measured vitrinite reflectances

53 and well temperatures if higher or lower heat flows are used. The amount of uplift for each well was then calibrated against measured vitrinite reflectance to create a map of removed overburden that was used in the burial history modeling. The Bush Federal #1 well shows the good match between the modeled uplift of 4500 feet (1370 meters) and the measured vitrinite reflectances in the well. The GENESIS-derived estimates of Tertiary uplift are similar to estimates derived from apatite fission track analysis and sonic velocity surveys that are not reported here (S. Bergman et al., written comm. 1994). Because of the uncertainties involved in calibrating to Ro measurements that may have been affected by suppression of vitrinite reflectance (Price and Barker, 1985), recycled vitrinite, or cavings from shallower intervals in cuttings samples, the removed overburden map is only considered accurate within ? 1000 feet (? 300 meters) in the study area. The results of the GENESIS 1D models were used in EXODUS to construct a map-based burial history reconstruction. The advantage of EXODUS map-based reconstructions is that the entire mapped area is modeled, not just individual wells, and volumes and migration directions of generated hydrocarbons can be quickly calculated. The disadvantage is that variations in heating rate and surface temperature with time cannot be accounted for in the current version of the software, so the EXODUS model does not match the 1D GENESIS models in all areas. Regional structure maps on six horizons (Figure 3.4) were combined with the kerogen transformation curves in EXODUS to identify oil kitchens and to identify paleo-migration paths. Structure maps were constructed solely from well control and do not incorporate any seismic data. Structural tops for four of the horizons (Lisburne Group, Sag River Sandstone, Kuparuk River Formation, and West Sak sands) were picked primarily from well log correlation, and the remaining two horizons (Paleocene and Middle Eocene) were picked primarily from biostratigraphic data. The top of the Paleocene interval is picked at or near the first occurrence of Paraalnipallenites sp. (angiosperm pollen), and the Middle Eocene top is picked at or near the first occurrence of the marine dinoflagellate cyst Wetzeliella (J. Bennett, written comm. 1979; according to J. G. Watkins (written comm. 1982), Wetzeliella may extend into Early Oligocene time). Lithostratigraphic correlations were used if biostratigraphic data were not available. The top of the Paleocene interval is approximately equivalent to the lithostratigraphic top of the Staines Tongue of the Sagavanirktok Formation, and the top of the Middle Eocene interval is approximately equivalent to the lithostratigraphic top of the Mikkelsen Tongue of the Canning Formation (Molenaar et al., 1986). EXODUS displays the hydrocarbon migration pathways from the source kitchens and calculates the volume of oil expelled within the fetch area of decompacted paleostructure maps. Expelled oil volumes are calculated from source rock initial potential (S2), source rock transformation ratio (TR), source rock total organic carbon (TOC), source rock thickness (H), area (A), and bulk source rock density (?rock) with the equation Expelled oil volume (barrels) = 6700*((S2*TR) TOC)*H*A*?rock (1)

where the units are: 6700 barrels/m km2 (assumes that the weight of 6.7 barrels of oil is a metric ton), S2 (mg hydrocarbons/g rock), TR (dimensionless), TOC (weight %), H (meters), A (square kilometers), and ?rock (g/cc). The S2 measurement is defined as the weight of hydrocarbons per

54 gram of rock generated during heating in a Rock Eval instrument, and measures the potential to generate hydrocarbons during thermal maturation (Jarvie, 1991). TOC is calculated from Rock Eval measurements (Jarvie, 1991). The values of S2 and TOC that were used to calculate expelled volumes from each source rock are the average values for immature cores in the study area (Tables 1.1, 3.1). The transformation ratio in the EXODUS model is a function of burial depth for each source rock and varies between 0 (source rocks that have not been heated enough to generate any hydrocarbons) and 1 (source rocks that are totally spent). Transformation ratios through time at all modeled well locations were calculated in the GENESIS 1D burial history models using custom kinetic models for each source rock. The transformation ratios in the EXODUS maps were then matched with 1D GENESIS transformation ratios in the modeled wells. The TOC is subtracted from the generated hydrocarbons in equation 1 under the assumption that 100 mg of hydrocarbons will be absorbed upon each gram of organic carbon and will not be expelled from the source rock. This assumption is only an approximation because absorption will vary with temperature and pressure (Gaschnitz et al., 2000). On Figure 3.5, the line labeled S1/TOC=1 corresponds with an absorption of 100 mg hydrocarbons per gram of organic carbon. The Rock Eval S1 measurement of free and absorbed hydrocarbons is made on samples at surface conditions, however, so it is not a direct measure of the subsurface concentration of hydrocarbons in the source rock because hydrocarbons will be expelled as the rock is brought to the surface (Price, 1989). Correction to subsurface conditions would require increasing the measured Rock Eval S1 value by a factor of about 1.3 for a typical oil in the 25 - 400 API gravity range (A. Brown, written comm. 1996). The corrected S1 would reduce the surface measured S1/TOC value to about 0.75 for a subsurface absorption of 100 mg hydrocarbons per gram organic carbon. For the most part, the North Slope source rocks on Figure 3.5 have S1/TOC ratios equal to or less than 0.75 at high TOC values, and the S1/TOC values greater than 0.75 (e. g. the HRZ core samples from Hemi Springs #3 well) could arguably be attributed to contamination by drilling mud or to migrated hydrocarbons in the pore spaces of the rock. Other studies have concluded that absorption of hydrocarbons by kerogen is less than or equal to 200 mg/g of organic carbon (Pepper, 1992), and that North Slope source rock S1/TOC values greater than 1 indicate the presence of migrated hydrocarbons (Magoon and Claypool, 1984). One of the counter-intuitive results of equation 1 is that increasing the TOC of a source rock in the EXODUS model without increasing its S2 value will result in a decrease of expelled oil volume in the model due to increased hydrocarbon absorption on the higher organic carbon content of the source rock. Expulsion does not begin in the model until enough oil has been generated to exceed the threshold absorption of 100 mg hydrocarbons/g organic carbon. The thickness H for each source rock is derived from isopach maps in the EXODUS model (Figure 3.6). The Shublik Formation has been cored in a number of wells and its depositional thickness varies from a low of 50 feet (15 meters) at the Prudhoe Bay Field to a high of 250 feet (75 meters) beneath the Colville Delta in the northwestern part of the study area. The thickness of the Kingak Shale source interval is not well constrained from core data because typically only the lowermost part of the Kingak Shale was cored in order to recover the top of the Sag River Sandstone. Well logs indicate that the Kingak low-density, low-velocity source interval thickness varies from 130 to 400 feet (40 to 120 meters) in the study area (Figure 1.5). The thickest Kingak source interval lies beneath the Colville Delta in the northwestern part of the study area. In the

55 eastern and extreme northwestern parts of the study area the Kingak Shale and the Shublik Formation were removed by erosion beneath the Lower Cretaceous Unconformity (LCU). The source rock thickness for the HRZ Formation was estimated from the thickness of persistent gamma ray log readings greater than 150 API units. The HRZ Formation has a relatively constant thickness over most of the study area, varying from 130 to 200 feet (40 to 60 meters). The only exception is the area north of the Prudhoe Bay Field, where the HRZ Formation was removed by Late Cretaceous erosion. It is likely that the HRZ Formation is present north of the barrier islands beneath the Beaufort Sea, but there are no wells to confirm its existence and consequently no HRZ-sourced oil volumes were calculated north of the isopach map limits. Source rock densities of 2.4 (HRZ), 2.5 (Kingak), and 2.6 (Shublik) g/cc were derived from bulk density wireline log measurements (Figure 1.5) and are assumed as constants in equation 1. Migration directions for oil expelled from each source rock were assumed to be parallel to structural dip in the EXODUS models. Paleostructure maps on the top Kuparuk Formation were used to model hydrocarbon migration directions from HRZ source rock. In areas where the Kuparuk Formation is missing, migration is assumed to occur along the Lower Cretaceous Unconformity (LCU) surface. The base of the HRZ Formation is typically 100 feet (30 meters) shallower than the top of the Kuparuk Formation except in the eastern part of the study area where the HRZ Formation directly overlies the LCU. Paleostructure maps on the top Sag River sandstone were used to model hydrocarbon migration directions from the overlying Kingak and underlying Shublik source rocks. In the southern part of the study area where the Sag River sandstone is not present, the top of the Shublik Formation was used instead of the Sag horizon to model Kingak and Shublik migration. In the eastern part of the study area where both Kingak and Shublik source rocks are truncated by the LCU, the expelled Shublik/Kingak oil is assumed to continue to migrate along the unconformity surface. KINETIC MODELS FOR HYDROCARBON GENERATION Custom kinetic parameters for Shublik, Kingak, and HRZ source rocks were measured in order to constrain the timing of hydrocarbon generation. Samples selected for measurement of kinetic parameters were taken from the least mature cores available in the study area. The Shublik core samples were taken from distal calcareous facies at the Phoenix #1 well and from shaly facies in the M-07 and 12-03 wells at Prudhoe Bay Field (Figures 3.1, 3.7; Table 1.1). Measured vitrinite reflectances in the Phoenix #1 Shublik core range from 0.63% to 0.75% Ro (average 0.70% Ro; Table 3.2). These vitrinite reflectance measurements are lower than the 0.76% to 0.80% Ro range previously reported by Robison et al. (1996) for the Phoenix #1 Shublik core, but more closely match the average 0.74% equivalent vitrinite reflectance (VRMPI and VR20S) calculated from MPI-1 and C29-sterane 20S/20R maturity parameters in Phoenix core extracts (Table 1.2). Rock Eval maturity parameters Tmax and production index (PI) indicate that the Shublik interval has not generated significant quantities of hydrocarbons at the Phoenix #1 location (Figure 3.8). Maturity data suggest that the Shublik Formation has generated oil within the western part of the Prudhoe Bay Field. Vitrinite reflectance measurements in the Shublik Formation and Kingak Shale vary from 0.46% to 0.76% in Prudhoe Bay cores, similar to the range in Phoenix #1 core (Figure 3.9). However, the average Tmax of 4360C for M-07 Shublik core and 4300C in 12-03 Shublik core is higher than the 4260C average Tmax in Phoenix #1 Shublik core. Some of this

56 Tmax discrepancy may reflect geochemical differences between Shublik shaly facies at Prudhoe Bay Field and calcareous facies at Phoenix #1 rather than differences in maturity. However, the range in Tmax is similar to the range in present-day temperatures of the Shublik Formation in the wells (Table 3.2), so the Tmax differences probably reflect real differences in temperature history and suggest that the Shublik Formation has entered the oil window at the western edge of Prudhoe Bay Field. The Shublik Formation at the West End of Prudhoe has previously been reported to be at peak oil generation based on measured thermal alteration indices (TAIs) of 2.7 to 2.8 (Seifert et al., 1980). Additional measurements of TAI in this study confirm a range of 2+ to 3 at the Prudhoe West End but suggest lower maturities in the eastern part of the field at the 12-03 well, which has TAI values of 2- to 2 (J. Castao, written comm. 1997). These observations are consistent with the observed temperature gradient from 800C to 1100C from east to west across Prudhoe Bay Field (Figure 3.7), and suggest that the Shublik Formation is immature in the northeastern part of the field and enters the oil window in the western part of the field. The Kingak samples selected for kinetics analysis were taken from the lower part of a Kingak Shale core in PBU U-13 (originally named Term Well B) at Prudhoe Bay Field and from cuttings in the Kalubik #1 well northwest of the Kuparuk Field. The vitrinite reflectance of the Kingak interval in the U-13 core averages 0.73% Ro. Tmax values for the Kingak Shale in the PBU U13 well are slightly higher than Tmax values for the underlying Shublik interval (Figure 3.8), consistent with kinetics measurements that indicate that the Kingak Shale generates hydrocarbons at higher temperatures than the Shublik interval (discussed below). The higher Tmax of Kingak source rock relative to Shublik source rock in the PBU U-13 well cannot be caused by maturity differences because the Kingak interval is shallower than the Shublik interval, and illustrates the influence of kerogen type upon Tmax measurements. The Kalubik #1 Kingak sample has an early oil window maturity based upon its Production Index (PI) of about 0.1 and its Ro of 0.78%. HRZ Formation kinetic parameters were measured on a core sample from the Hemi Springs State #3 well south of Prudhoe Bay Field and on cuttings from the Phoenix #1 well. The measured vitrinite reflectances are 0.7% in the Hemi Springs #3 core and 0.6% in the Kalubik #1 cuttings. Tmax and PI values are consistent with early oil window maturities in both samples. The relatively high PI measured in some of the Hemi Springs #3 samples indicates the presence of migrated hydrocarbons and is also evident on the S1 versus TOC plot (Figures 3.5, 3.8). The estimated present-day temperatures at the depths of the source rock kinetics samples range from 900C at the Phoenix well to 1050C at the M-07 and U-13 wells in the Prudhoe Bay Field (Table 3.2; Figure 3.7). GENESIS 1D models predict higher paleo-temperatures of up to 1150C in the M-07 and U-13 wells at maximum burial depths prior to Tertiary uplift. The modeled maximum temperatures at the M-07 and U-13 wells are higher than the 1000C temperature that some researchers believe is the minimum required for oil generation (Cooles et al., 1986; Mackenzie et al., 1987; Quigley and Mackenzie, 1988; Pepper, 1992). In addition, a temperature of 1150C corresponds to the calculated onset of 10% transformation for calcareous Shublik facies at heating rates of 0.50C per million years, as discussed below. It is therefore likely that the M-07 Shublik core sample has already generated some hydrocarbons and is unsuitable for

57 kinetics analysis, because the calculated temperature for the onset of oil generation will be too high (Tissot et al., 1987). In order to graphically illustrate the differences in timing of hydrocarbon generation between the source rocks, a constant heating rate of 10C per million years was used in the LLNL KINETICS program (Burnham et al, 1987; Braun and Burnham, 1994) to calculate kerogen transformation as a function of temperature with discrete activation energy distributions (Figure 3.10). The 10C/my heating rate is typical for the burial history of source rocks in the oil kitchen south of Prudhoe Bay Field (Figure 3.3). The calcareous facies of the Shublik Formation begins to generate hydrocarbons earlier than the other source rocks, reaching 10% transformation at a temperature of about 1200C (Figure 3.10). A lower heating rate of 0.50C/my decreases the temperature required for hydrocarbon generation from calcareous Shublik source rock by about 50C. The kerogen in calcareous Shublik facies is sulfur-rich and transforms to hydrocarbons at lower temperatures than shaly Shublik facies, Kingak, and HRZ source rocks because sulfurcarbon chemical bonds break more readily under thermal stress than carbon-carbon bonds (Orr, 1986; Tegelaar and Noble, 1994). Shaly Shublik source rock core from the 12-03 well has a lower sulfur concentration than the calcareous Shublik facies (Table 3.2) and apparently generates hydrocarbons at about 100C higher temperature, reaching 10% TR at about 1250C. It is likely that the M-07 core is more mature than the Phoenix #1 core, as discussed above, and that the delayed onset of generation in the M-07 Shublik sample is an artifact of sample maturity. However, the 12-03 core has been subjected to an estimated maximum temperature of only 1050C (Table 3.2) yet also generates hydrocarbons at a higher temperature than the Phoenix #1 calcareous Shublik facies (Figure 3.10). The similar kinetic responses of M-07 and 12-03 shaly Shublik facies suggest that the delayed onset of hydrocarbon generation in shaly Shublik facies relative to more sulfur-rich, calcareous Shublik facies is not entirely an artifact of sample maturity. Both HRZ samples reach 10% transformation at about 1250C (Figure 3.10). The Kingak Shale samples require significantly higher temperatures than the HRZ samples in order to generate hydrocarbons, reaching 10% TR at 1400C. Kingak kerogen has a lower sulfur concentration, as evidenced by its low thiophene ratio (Table 3.2; Tegelaar and Noble, 1994), and also exhibits a narrow activation energy distribution. Braun et al. (1991) believe that the Gaussian or Tmax shift kinetic model provides the best parameters for extrapolation to geologic heating rates for samples with a narrow activation energy distribution like the Kingak Shale samples. Application of the Gaussian model to the Kingak Shale sample from the Kalubik #1 well results in a 100C lower temperature for the onset of hydrocarbon generation, more in line with the HRZ and shaly Shublik kinetic models (Figure 3.10). Use of a Gaussian kinetic model for the Phoenix #1 Shublik sample would reduce its 10% transformation temperature by about 50C to 1150C. The Kingak Shale Gaussian kinetic parameters from the Kalubik #1 well were used to model generation from the Kingak Shale because the Gaussian model provides a better match to the observed distribution of Kingak-sourced oils in the study area. Because of the possible oil window maturity of shaly Shublik facies at Prudhoe Bay Field, the kinetic parameters from the calcareous Shublik facies at the Phoenix #1 well were used to model Shublik generation throughout the study area. However, values of S2 and TOC from shaly Shublik facies were used

58 instead of higher calcareous Shublik values to calculate volumes of oils generated within Prudhoe Bay Field and to the north. Kinetic parameters for the HRZ Formation were taken from the Hemi Springs #3 core sample. The gas windows on the EXODUS burial history reconstructions correspond to areas where modeled temperatures of the source rocks exceed 1800C. Compositional kinetics parameters for gas generation have not been measured on the source rocks in this study, and the current version of EXODUS software does not have the capability to calculate gas volumes. The assumed 1800C temperature for oil-gas cracking corresponds to a modeled vitrinite reflectance of about 1.5% for Shublik and Kingak source rocks in the Bush Federal #1 well. A Ro value of 1.5% corresponds to peak gas generation in the GENESIS 1D model of the Bush Federal well (Figure 3.11). In the GENESIS models, gas generation from all source rocks was modeled to occur in response to oil cracking in the source rocks using a single activation energy of 55.28 kcal/mole and a preexponential frequency factor of 1.0E + 13, similar to the values suggested by Quigley and Mackenzie (1988). Various temperatures for the onset of oil to gas cracking ranging from 1400C to 1700C have been proposed for different oils (Quigley and Mackenzie, 1988; Pepper, 1992; Schenk and Horsfield, 1995). Waples (2000) calculates that at a geologic heating rate of 10C/my, the maximum temperature for preservation of oil in reservoirs ranges from 174 to 1780C, similar to the 1800C cutoff used in the EXODUS reconstructions in this study. PETROLEUM FILLING HISTORIES LOWER CRETACEOUS UNCONFORMITY Ellesmerian sequence reservoirs and source rocks were uplifted and eroded during Beaufortian rifting in Early Cretaceous time, and the resulting Lower Cretaceous Unconformity (LCU) surface connects Shublik, Kingak, and HRZ source rocks with the Ivishak and Kuparuk reservoirs in the Prudhoe Bay Field area (Figures 3.12, 3.13). Numerous northwest-striking and east-striking normal faults displaced the Sag/Ivishak and Kuparuk lower member reservoirs during the Beaufortian rifting event (Figures 3.12, 3.14). Syndepositional thickening of the Kuparuk Formation upper member occurred along the downthrown sides of these faults in the Kuparuk and Point McIntyre Field areas (Masterson and Paris, 1987), and a thin but widespread transgressive lag sandstone is frequently present along the LCU surface. Several authors have postulated that Early Cretaceous fluid incursion along the LCU surface created enhanced permeability through dissolution of diagenetic cements in the underlying intervals, which would enhance migration along the LCU (Barnes, 1987; Woidneck et al., 1987; Shanmugam, 1985; Jameson, 1994). Sag, Ivishak, and Lisburne reservoirs are truncated by the LCU at the eastern edge of the Prudhoe Bay Field and are directly overlain by HRZ source rock (Figure 3.13). LATE CRETACEOUS (66 MA) RECONSTRUCTION In Late Cretaceous time, Brookian sedimentation pushed the Shublik Formation into the oil window within 12 miles (20 km) of the Prudhoe Bay Field (Figure 3.13). Campanian and Maastrichtian sediments were eroded from the Brooks Range and prograded northeast into the Colville Trough foreland basin, culminating in deposition of the West Sak sandstones in a shallow marine shelf environment in the Kuparuk/Prudhoe Bay Field area (Werner, 1987; Figures 3.15, 3.16b). The Prudhoe Bay Field seal did not form until after deposition of the HRZ

59 Formation and overlying Upper Cretaceous shales of the Colville Group. An estimated 109 billion barrels of oil were expelled from Shublik source rock in the study area during Late Cretaceous time, 71 billion barrels of which were within the fetch area of the Prudhoe Bay paleoclosure. The Late Cretaceous paleo-closure at the future site of the Prudhoe Bay Field was larger than the present-day field area and was oriented in a northwest/southeast direction along the strike of the LCU truncation of the Sag and Ivishak reservoirs (Figure 3.16b). Temperatures in the southwestern part of the study area are modeled to exceed 1800C in Late Cretaceous time, high enough to cause oil to gas cracking in the southwestern corner of the study area. This gas could have enhanced the migration efficiency of Shublik-sourced oil by displacing previously filled oil accumulations and spilling oil updip towards the Prudhoe Bay paleo-closure in the manner suggested by Gussow (1954). An estimated 14 billion barrels of Kingak-sourced oil and 17 billion barrels of HRZ-source oil were expelled in the southwestern corner of the study area and migrated towards the Prudhoe Bay paleo-closure. Because the Shublik and Kingak source rocks are older and more deeply buried than the HRZ Formation, the first oil to migrate to the Prudhoe Bay paleo-trap would have been generated from the Shublik and Kingak intervals. Cracking of Shublik-sourced oil to gas would have occurred at about the same time that the overlying HRZ Formation entered the oil window (Figure 3.3). Geochemical evidence from residual oil in the Prudhoe Bay Field gas cap suggests that a Shublik/Kingak/HRZ oil charge reached the field first, followed by a gas charge (Chapter 1). At the close of Late Cretaceous time the Prudhoe Bay paleo-trap was buried only 700 meters (2000 feet; Figure 3.13) and any early hydrocarbon charge could have been subjected to biodegradation. Prudhoe Bay Field oils contain 25-norhopanes that are interpreted as evidence for an early episode of biodegradation that was followed by a charge of unaltered hydrocarbons (Chapter 1). The Kuparuk/LCU paleo-closure covered a small area to the north of the present-day Prudhoe Bay Field (Figure 3.16a). HRZ-sourced oil migrating from the south could have entered any Kuparuk reservoirs deposited in this area because the HRZ Formation is in direct contact with the underlying Kuparuk reservoir (Figure 3.13). Oils tested from the Kuparuk reservoirs in this area show geochemical evidence for a HRZ co-source (e. g. N Kuparuk 26-12-12; Table 1.3). An additional 46 billion barrels of Shublik and Kingak-sourced oil was expelled west of the Prudhoe fetch area. The Kuparuk Field was located in an unfavorable position for Shublik oil charge during Late Cretaceous time because migration pathways diverged beneath the presentday field area, and because the Kuparuk Formation closure had not yet formed. In the eastern part of the study area, 6 billion barrels of Shublik and Kingak-sourced oil that was expelled in the southeast corner of the study area are modeled to migrate towards the LCU truncation surface southeast of the Prudhoe paleoclosure (Figure 3.16b). Once this oil reached the LCU truncation of the Shublik and Ivishak intervals, its migration pathway along the LCU surface is modeled to continue north towards the Barrow Arch (Figure 3.16a). A large quantity of additional oil, perhaps as much as 80 billion barrels, may have also reached the eastern Barrow Arch from Shublik and Kingak source rocks that fall outside of the study area to the southeast.

60 MIDDLE EOCENE (45 MA) RECONSTRUCTION The Brookian sedimentary depocenter shifted to the southeast during Paleogene time, probably in response to a 62 Ma Paleocene uplift event in the ANWR (OSullivan et al., 1993; Figure 3.15). The direction of maximum horizontal compressive stress is inferred to have shifted from north-south during Maastrichtian/Campanian time to northwest-southeast during Paleocene time in response to the change in regional stress fields caused by onset of thrusting in the ANWR. The shift in maximum horizontal stress direction may have allowed enhanced vertical hydrocarbon migration along reactivated northwest-striking rift-related faults along the Barrow Arch (Figure 3.14). Deltaic sediments of the Ugnu Formation were deposited in the Prudhoe/Kuparuk area during Paleocene time (Figure 3.17). The Middle Eocene reconstruction includes the thickness of removed overburden (Figure 3.4). In the model, the entire thickness of removed overburden is deposited at 45 Ma and is removed gradually until the present day. This is, of course, a gross oversimplification of the burial history. Some of the removed overburden likely comprised Late Cretaceous and Paleocene sediments that were deposited prior to 45 my, and erosion could have begun as early as Paleocene time in the southwestern part of the study area. The Middle Eocene reconstruction should therefore be considered as the maximum burial depth model, with the caveat that maximum burial did not occur simultaneously throughout the study area. Nevertheless, the present-day structural dip of the Wetzeliella marker and the outcrop patterns of Upper Cretaceous, Paleocene, and Middle Eocene sediments (Figure 3.4) suggest that much of the overburden was removed during postMiddle Eocene uplift of the southern and western part of the study area. Apatite fission track measurements in the ANWR suggest a rapid uplift event at about 45 Ma (Middle Eocene) and slower uplift in Late Eocene - Middle Oligocene time between 40 and 30 Ma (OSullivan et al., 1993). Twenty-four billion barrels of Shublik-sourced oil and 8 billion barrels of Kingak-sourced oil migrated towards the Prudhoe Bay Field paleoclosure from the south in the Middle Eocene reconstruction. The Shublik oil window reached the western edge of the present-day Prudhoe Bay Field (Figure 3.18b). Some Shublik oil began to be generated north of the Prudhoe paleoclosure, but most of this northern oil kitchen falls outside the boundaries of the model and is not accounted for. An additional 31 billion barrels of HRZ-sourced oil migrating from the south resulted in a cumulative total of 160 billion barrels of Shublik, Kingak, and HRZ-sourced oil expelled within the Prudhoe Bay fetch area from Late Cretaceous to Middle Eocene time. An additional 12 billion barrels of Shublik-sourced oil that migrated towards the Barrow Arch along the LCU in the model may have also reached the Prudhoe Bay paleo-trap but is not included in the total for the Prudhoe fetch area because of the circuitous path necessary to reach the field (Figure 3.18b). Shublik source rock directly beneath the Kuparuk Field entered the oil window between Paleocene and Middle Eocene time in the model (Figure 3.18b), and structural closures began to form in the overlying Kuparuk Formation in Middle Eocene time (Figure 3.18a). The calcareous facies of the Shublik Formation is assumed to underlie the Kuparuk Field in the model, although there are no conventional cores available to verify the presence of calcareous facies except for the Colville #1 Shublik core located about 5 miles (8 km) west of the field (Chapter 1). The

61 volume of Shublik-sourced oil expelled directly beneath the present-day outline of the Kuparuk Field is 6 billion barrels in the model, which matches the estimated 6 billion barrels of oil in place in the field. The modeled onset of oil generation at 10% transformation ratio in the Kingak Shale occurs beneath the southwestern corner of the Kuparuk Field, where geochemical evidence in Kuparuk oils suggests possible dilution of the Shublik charge with a Kingak co-source (Chapter 1). The coincidence of the interpreted Shublik charge with the underlying maturity of the Shublik source rock suggests that migration may be predominantly vertical beneath the Kuparuk Field. Numerous northwest-striking faults connect the Kuparuk reservoir with the underlying Shublik and Kingak source rocks in the Kuparuk Field area (Figure 3.14). Although the paleo-stress field beneath the Kuparuk Field is a matter of conjecture, the direction of maximum principle horizontal stress may have been oriented sub-parallel to the northweststriking faults beginning in Paleocene time (Figure 3.15), allowing vertical oil migration from Shublik and Kingak source rocks into the overlying Kuparuk reservoir. Alternatively, the northwest-striking fault system may not have been open to vertical oil migration until postMiddle Eocene uplift and eastward tilting, at which time oil that was previously trapped in Sag and Ivishak fault blocks beneath the Kuparuk Field may have remigrated up the fault planes into the Kuparuk reservoir. Further evidence for vertical oil migration is provided by the chemistry of oils tested west of the Kuparuk Field. The oil tested from the Kuparuk reservoir in the Kalubik #1 well is an excellent chemical match with Shublik calcareous source rock facies with an interpreted 100% Shublik source (Chapter 1) and is located above the Shublik oil window but outside of the Kingak oil window (Figure 3.18b). The Fiord #1 well is located further downdip where both the Shublik and Kingak source rocks are in the oil window in the model, and its Kuparuk oil exhibits intermediate geochemical properties indicative of a mixture co-sourced by both the Shublik and Kingak Formations (Dzou, Holba, and Masterson, written comm. 1994; Chapter 1). Alpine Field is located in an area where the underlying Kingak Shale is still in the oil window but the Shublik Formation has reached an estimated maturity of 1.2% Ro (Figures 3.9, 3.18). GENESIS 1D models predict that at 1.2% Ro, gas will be generated from the Shublik Formation without much liquid (Figure 3.11). These model results provide a potential explanation for the interpreted Kingak source for Alpine oil and possible co-source of Shublik gas (Chapter 1), although a Kingak Shale source for Alpine gas cannot be ruled out based on currently available data. If the Gaussian kinetic model is not used to model Kingak oil generation, the position of the 10% Kingak transformation ratio would not extend as far to the north in the model, but would still place the Kingak source rock in the oil window beneath the Alpine Field and the Fiord #1 well. The HRZ oil window reaches the southern boundary of the Tarn Field during Middle Eocene time in the model (Figure 3.18a). Tarn oil is a good geochemical match with HRZ source rock (Chapter 1). The Cenomanian deep water deposits that include the Bermuda Sandstone reservoir at Tarn Field downlap HRZ source rock to the east, providing a potential stratal migration path for Tarn oil. The Shublik Formation source rock has an estimated maturity of 1.2% Ro beneath Tarn Field, and the isotopic composition of Tarn gas is consistent with generation from the Shublik Formation (Chapter 1). An HRZ source is also interpreted for the biodegraded Kuukpik #3 oil that was tested from a shallow Cretaceous reservoir (Chapter 1). Although the Kuukpik #3 well is located north of the modeled HRZ oil window, it is located within a modeled migration pathway from the HRZ oil kitchen (Figure 3.18a).

62 At maximum burial during Middle Eocene time, the Lisburne Group was heated to temperatures exceeding 1500C throughout the entire southern half of the study area (Figure 3.19). Generation of CO2 from reaction between dolomite and kaolinite in the Lisburne Group can begin at 1500C (Muffler and White, 1968; Chapter 1). The modeled Lisburne 1500C isotherm during Middle Eocene time is within a few miles of the 2F-20 well that tested 17% CO2 in gas from the Lisburne reservoir beneath the Kuparuk Field (Chapter 1). An enormous area of CO2 generation covering at least 2000 square miles (5000 square kilometers) is modeled for the Lisburne Group within the fetch area of the Prudhoe paleo-closure. Additional CO2 and methane would have been generated deeper in the Colville Trough to the south of the study area. If it is assumed that oil cracks to gas at temperature exceeding 1800C, the model places Lisburne dry gas generation about 25 miles (40 kilometers) south of the Prudhoe Bay Field in Middle Eocene time. Carbon dioxide may have migrated with Lisburne-sourced hydrocarbons as a miscible phase, reducing its fugacity and partially shielding it from interaction with wall rock along the migration path to Prudhoe Bay Field (J. W. Bielack and A. Brown, written comm. 1986). PRESENT DAY Between Middle Eocene time and the present day, the study area was tilted 1-20 to the northeast, as evidenced by the present-day structural dip on the top of the Middle Eocene, Paleocene, and West Sak intervals (Figure 3.4). Two episodes of rapid uplift in the ANWR occurred in Middle Eocene time (~45 Ma) and in Miocene time (~ 23 Ma), and another slower phase of uplift occurred during Late Eocene and Oligocene time (~40-30 Ma; OSullivan et al., 1993). Bird (1985) suggested that most of the uplift between the Colville and Canning Rivers occurred during Oligocene time. It is possible that uplift occurred episodically in response to thrusting in the ANWR, and that the direction of tilting in the study area migrated from southeast during Paleocene time to northeast today as the thrust front migrated from south to north in the ANWR (OSullivan et al., 1993). The orientation of north/northeast-striking faults suggests that the initial direction of tilting was towards the southeast, approximately parallel to the inferred direction of maximum horizontal stress during Paleocene time (Figure 3.15). North/northeaststriking faults that are downthrown towards the southeast outnumber faults that are downthrown to the northwest by a ratio of 5:1 in the Kuparuk Field area, consistent with their formation during post- Eocene uplift and tilting (Masterson and Paris, 1987). Spillage of oil from the Prudhoe Bay Field to the West Sak Field likely began when eastward tilting began to reduce the paleo-closure at Prudhoe from 2000 feet (600 meters) to the presentday hydrocarbon column of 1000 feet (300 meters). Carman and Hardwick (1983) suggested that spillage to the West Sak Field occurred along the Eileen fault trend at the extreme western end of the Prudhoe Bay Field. However, the geochemical composition of the Prudhoe Bay West End oils is not identical to the Prudhoe Bay main field oils, and the Sag and Kuparuk reservoirs that overlie the Ivishak reservoir in the West End contain oils with unique geochemistries (Chapters 1, 2). If billions of barrels of oil spilled along the Eileen fault trend from the Prudhoe main field as suggested by Carman and Hardwick (1983), the West End Ivishak oils should be identical to Prudhoe main field oils and to oils in overlying reservoirs along the Eileen fault spill path. A more plausible spill path is from the Prudhoe Bay main field, where West Sak accumulations at S, M, and W pads in the northwestern corner of the main field are trapped downdip of the Eileen

63 fault (Figures 1.4, 3.14c). From this spill point at the western edge of the Prudhoe Bay main field, oil that entered the West Sak reservoir is modeled to migrate updip to the West Sak Field. A spill point east of the West End provides an explanation for the geochemical similarities between Prudhoe Bay main field oils and West Sak Field oils (Chapter 1). Spillage of oil from the Prudhoe Bay main field to the West Sak Field could have occurred along faults that connect the Ivishak and West Sak reservoirs (Figure 3.14c). The HRZ Formation is an excellent seal for the Prudhoe Bay accumulation, and capillary pressure measurements on HRZ core indicate that an oil column of at least 3500 feet (1075 meters) would be required to cause capillary seal failure. Because the thickness of hydrocarbon column required to cause HRZ capillary seal failure is greater than the maximum paleo-closure and oil column height at Prudhoe, seal failure most likely occurred along faults and fractures that connect the Ivishak and West Sak reservoirs. Both north/northeast-striking faults and northwest-striking faults displace the entire section between the Ivishak and West Sak intervals in the western part of the Prudhoe Bay main field. In contrast, only north/northeast-striking faults displace the section between the West Sak and Ivishak sandstones in the Kuparuk Field area, and the older northwest-striking faults do not reach the West Sak interval (Figure 3.14c). This difference in West Sak interval fault orientation between the two areas provides a possible explanation for why oil spilled from the Prudhoe accumulation into the overlying West Sak interval, but only gas leaked from the Kuparuk Field into the overlying West Sak Field (Chapter 2). North/northeast-striking faults would have been oriented perpendicular to the inferred Paleocene direction of maximum horizontal compressive stress and may have had lower fault plane permeability to hydrocarbon migration than northwest-striking faults that were oriented parallel with the inferred maximum stress. In addition, the presence of several intersecting faults connecting the West Sak and Ivishak reservoirs in the Prudhoe area may have created enhanced fault plane permeabilities and allowed migration of oil in areas where the fault sets intersect. Finally, there is about 2500 feet (775 meters) of mudstone seal separating the Kuparuk and West Sak reservoirs at the Kuparuk Field, but only 1500 feet (450 meters) separating the Ivishak and West Sak reservoirs at Prudhoe Bay Field (Figure 3.17). All of these factors may have contributed to spillage of oil at Prudhoe Bay Field but only gas and condensate at Kuparuk Field. Post-Eocene tilting resulted in uplift and erosion of the West Sak interval in the area west of the Kuparuk Field and allowed influx of fresh, meteoric water to the subsurface (Figure 3.4). West Sak formation water salinities decrease updip towards the surface (Werner, 1987) and the hydrogen isotopic composition of West Sak water is extremely depleted, like the surface waters of the North Slope (Chapter 2). Biodegradation of West Sak oil could have occurred under aerobic conditions as oil spilled from the Prudhoe Bay Field, migrated updip, and displaced oxygenated meteoric water in traps at the West Sak Field. Subsequent leakage of gas and condensate from the underlying Kuparuk Field could have occurred along northeast-striking faults that connect the Kuparuk and West Sak reservoirs, possibly in response to fault movement caused by episodic thrusting in the ANWR (OSullivan et al., 1993). The secondary gas/condensate charge was lightly biodegraded in the shallowest West Sak reservoirs, possibly under anaerobic conditions because the secondary gas/condensate charge accumulated in a previously biodegraded oil and would have had limited contact with meteoric water (Chapter 2).

64 Methane in West Sak solution gas was generated by CO2 reduction under anaerobic conditions (Chapter 2). Eastward tilting also created the structural closure at the West End of the Prudhoe Bay Field in the model. Post-Eocene formation of the West End structural closure could explain the reduced reservoir quality in the West End Ivishak sandstone reservoir relative to the main field (Wadman et al., 1979). If hydrocarbon migration into the Prudhoe Bay main field paleo-closure began in Late Cretaceous time as suggested by the model, diagenesis and cementation in the main field Ivishak reservoir may have been inhibited due to the presence of hydrocarbons. Cementation would have continued to reduce Ivishak Sandstone reservoir quality in the West End reservoir until hydrocarbons migrated into the West End structure at greater burial depths in post-Eocene time. Post-Eocene burial resulted in modeled migration of relatively small quantities of oil in the study area (Figure 3.20). The positions of the oil and gas windows on Figure 3.20 correspond to the maximum burial depths experienced by the source rocks and have not been "rolled back" to account for cooling associated with structural uplift. Five billion barrels of additional oil from Shublik and Kingak source rocks migrated towards the Prudhoe Bay Field in the model, mostly from the north. Oil trapped in the newly formed closure at the Prudhoe Bay West End could have migrated in from the north, or could have been generated from Shublik source rocks that are modeled to enter the oil window in the West End and surrounding area. Some oil in the West End Ivishak reservoir may have also spilled from the main field, which would account for the HRZ co-source to West End Ivishak oils (Chapter 1). The Sag River Sandstone reservoir in the West End must have experienced a separate filling history from the Ivishak reservoir because the Sag oil is co-sourced from the Shublik and Kingak intervals with no HRZ co-source (Chapter 1). Kingak Shale source rock is not modeled to be in the oil window at the Prudhoe West End, so if the model is correct then the interpreted Kingak co-source in the West End Sag River Sandstone reservoirs must have migrated laterally from oil kitchens to the north or south. An additional 3 billion barrels of oil from the HRZ Formation is modeled to migrate towards the Prudhoe Bay Field from the east. Post-Eocene tilting destroyed the large Kuparuk Formation paleo-structural closure at the northern part of the Prudhoe Bay Field, and could conceivably have spilled oils to the Kuparuk Field closure to the west. However, the presence of HRZ cosource in Kuparuk Formation oils in the Prudhoe Bay Field area and lack of HRZ co-source in Kuparuk Field oils indicates that large amounts of oil from the Prudhoe paleo-trap probably did not spill eastwards into the Kuparuk Field (Chapter 1). Formation of the Prudhoe Bay main field tar mat likely began when the Paleogene gas charge arrived and began to deasphalt the accumulation, and continued as the oil-water contact swept upward through the reservoir during post-Eocene burial, tilting, and spillage. There is a zone of heavy oil at the base of the Prudhoe oil column (Figure 1.19) that would have come into contact with any late gas charge that entered the Ivishak reservoir at the oil-water contact. Tar mat formation may have been enhanced by thermal convection in the Prudhoe Bay oil column caused by the present-day 350C lateral temperature gradient in the field (Figure 3.7). Numerical modeling of this lateral temperature gradient suggests that thermal convection should turn over the oil column in the main field Ivishak reservoir in only 100,000 years (E. Y. Chang, written

65 comm. 1989). The cause of this temperature gradient is unknown but may be related to migration of hot fluids from the southern Colville Trough source kitchen into the field at the oil-water contact. Although this postulated thermal convection may have enhanced formation of the tar mat at Prudhoe by continually circulating oil to the oil-water contact, it is unlikely to be a critical factor because thermal convection does not occur in other accumulations with tar mats (Wilhelms and Larter, 1995). The volume of expelled hydrocarbons in the EXODUS model totals 168 billion barrels in the fetch area of the Prudhoe Bay Field from Late Cretaceous time until the present and consists of 59% Shublik co-source, 28% HRZ co-source, and 13% Kingak co-source (Table 3.3). If Kuparuk Field oils are assumed to represent pure Shublik-sourced oil, Tarn Field oils are assumed to represent pure HRZ-sourced oil, and Alpine Field oils are assumed to represent pure Kingak-sourced oil (Chapter 1), then the isotopic composition, API gravity, and sulfur content of the Prudhoe Bay main field oil accumulation almost exactly match the modeled oil composition in the Prudhoe Bay fetch area (Table 3.3). The correspondence between modeled and actual Prudhoe Bay main field oil compositions is remarkable, especially considering that the Prudhoe Bay trap was filled over a period of more than 65 million years from three different source intervals. These results suggest that despite the many assumptions and simplifications inherent in the EXODUS model, it nevertheless provides a powerful tool to predict the filling histories of prospects in undrilled basins and complex petroleum systems. SENSITIVITIES TO BURIAL HISTORY MODEL PARAMETERS The EXODUS model for the Prudhoe Bay Field fetch area is relatively insensitive to changes in the kinetic models for onset of hydrocarbon generation because the fetch area for the field does not change appreciably through time (Figures 3.16, 3.18). For example, changes to the Shublik kinetic parameters from calcareous facies to shaly facies produce at most a 10% change in the proportion of Shublik co-source to the field. The total volume of oil generated in the EXODUS model is also relatively insensitive to the kinetic parameters, but is more sensitive to the source rock density used in equation 1. Assumption of a constant source rock density of 2.2 g/cc for all three source rocks would decrease the total volume of expelled oil by about 20% in the Prudhoe fetch area, and could cause changes of up to 25% in modeled co-source proportions. Source rock thicknesses are relatively well constrained from logs through the Shublik and HRZ intervals, but the thickness and richness of the Kingak Shale source is more uncertain and could have a large effect on the modeled proportion of Kingak co-source. The initial potential of source rocks in the hydrocarbon kitchen south of Prudhoe is yet another source of uncertainty in the model. There are no cores of source intervals south of the Hemi Springs #3 well in the study area, so the initial potential to generate hydrocarbons in the kitchen must be estimated from cores of immature source intervals along the Barrow Arch. The timing of hydrocarbon generation and the position of the oil windows through time are highly dependent upon the temperature profile and timing of uplift in the models. A large volume of oil is generated in Late Cretaceous time in the model because the surface temperature is assumed to be 200C higher than the present day temperature. Addition of all the removed overburden at 45 Ma shifts oil that might have been generated in Late Cretaceous and/or Paleocene time into Middle Eocene time in the model. To a certain extent, adding the overburden

66 in Tertiary time compensates for the high modeled Cretaceous temperatures because if the removed overburden was added during Late Cretaceous time, almost all the oil in the study area would be generated prior to Tertiary deposition. On the other hand, if modeled temperatures in Cretaceous time are reduced down to Tertiary modeled levels and the removed overburden is added in Eocene time, most of the oil would be generated in Tertiary time. Because the fetch area for the Prudhoe Bay paleo-trap does not change appreciably from Late Cretaceous through Eocene time, the uncertainties in paleo-temperature and removed overburden thickness affect the timing of generation in the model but have little effect upon the total volume or co-source proportions of generated hydrocarbons delivered to the Prudhoe Bay Field. The oil volumes expelled in the model should be considered a minimum estimate because oil kitchens south and north of the study area are not included. Large volumes of oil, perhaps equal to the 100 billion barrels modeled from the Shublik, Kingak, and HRZ intervals during Late Cretaceous time, could have been generated in Early Cretaceous time south of the study area. This earlier charge could have contributed to the Prudhoe Bay accumulation if it reached the paleo-trap after deposition of sufficient mudstone seal above the Ivishak reservoir. To the north, the Shublik and Kingak source intervals are modeled to thin towards the paleo-shoreline, but the HRZ source interval may thicken in Early Cretaceous rift grabens offshore in the Beaufort Sea and could also contribute additional oil volumes to the modeled area. MIGRATION EFFICIENCY AND CARRIER BEDS The total volume of oil delivered to the Prudhoe paleo-trap consists of the estimated 25 billion barrels of oil in place at Prudhoe and the additional oil that was spilled from Prudhoe trap into the West Sak Field during Tertiary tilting. Estimates of West Sak oil in place range from 15 to 25 billion barrels (Werner, 1987), so the total volume of original oil in place at the Prudhoe Bay trap was at least 40 to 50 billion barrels. This estimate does not account for any oil that may have escaped to the surface or that spilled into other reservoirs or areas outside of the West Sak Field. The EXODUS model estimate of 168 billion barrels of oil delivered to the Prudhoe Bay Field indicates a migration efficiency of 25 to 30%. These estimates of migration efficiency are relatively high compared to published studies of other petroleum systems, but differ in two important aspects from typical estimates published in the literature. First, migration efficiency in this study is calculated from volumes of expelled oil, not generated oil, because the EXODUS model assumes that 100 mg of generated hydrocarbons will remain adsorbed to each gram of organic carbon and will not migrate out of the source rock (equation 1). Migration efficiencies in the literature are frequently quoted as percentages of generated oil (e. g. Schmoker, 1994) and would therefore be lower than the efficiencies quoted in this study. Unfortunately, the current version of EXODUS software does not calculate volumes of generated oil, so it is not possible to calculate migration efficiency from generated oil in this study. Secondly, migration efficiency in this study is calculated only within the boundaries of the fetch area of the Prudhoe Bay Field, not from the entire study area. The volume of oil generated in the entire study area is estimated at 273 billion barrels in the EXODUS model. Migration efficiency to the Prudhoe Bay trap would therefore drop to 15 - 18% if oil volumes outside the fetch area of the field were included in the calculation. If the postulated additional 100 billion barrels that may have migrated from the south into the study area are also considered, the calculated migration efficiency to Prudhoe would drop further to 11 - 13%.

67 Even when these differences in methodologies for migration efficiency calculations are taken into account, the migration efficiency in the Prudhoe Bay fetch area appears to be relatively high compared to other petroleum systems. Magoon and Valin (1994) list only one calculated migration efficiency greater than 14% in 16 documented petroleum systems. The relatively high migration efficiency to the Prudhoe trap likely reflects the fact that all three source rocks are in direct contact with the Ivishak and Sag River Sandstone reservoirs at the Prudhoe Bay Field, and that a Prudhoe paleo-trap with a large fetch area has existed since Late Cretaceous time. Bird (1994) estimates a migration efficiency of 1 to 2% for the entire North Slope Ellesmerian(!) petroleum system. Migration efficiency into the Kuparuk Field is 100% if it is assumed that all the oil in place was generated from Shublik source rock directly beneath the field. The EXODUS model calculates that 6 billion barrels of oil was expelled from Shublik source rock in the area beneath the field, and the estimated oil in place in the Kuparuk reservoir at the field is also 6 billion barrels. Additional oil was generated south of the field in the model, but the migration pathways for Shublik and Kingak-sourced oil diverged beneath Kuparuk Field prior to the present day (Figures 3.16, 3.18). The coincidence of formation of the Kuparuk Field closure with the entry of the underlying Shublik Formation into the oil window provides a plausible mechanism for highly efficient migration of oil into the Kuparuk Field along numerous northwest-striking rift faults that connect the source rock and reservoir (Figure 3.14b). These faults are oriented parallel to the inferred direction of maximum horizontal stress during Paleogene time (Figure 3.15), which may have enhanced the permeability along the fault planes and allowed vertical migration of oil. The younger set of north/northeast-striking faults at the Kuparuk Field probably did not form until post-Eocene uplift, and may have allowed leakage of gas from the Kuparuk Field to the overlying West Sak Field (Chapter 2). The present-day maximum horizontal in situ stress in the Prudhoe/Kuparuk area appears to be bimodal and varies from northwest to northeast (Hanks et al., in press). The present-day bimodal stress orientation could have resulted from extension along the northern Alaska continental margin, from interaction between the Barrow Arch and stresses generated by thrusting from the south and east, or from local stress perturbations on the Barrow Arch associated with complex fault patterns (Hanks et al., in press). An alternative model for filling the Kuparuk Field could invoke spillage of oil from Kuparuk Formation traps west of the field during Neogene uplift and eastward tilting. One problem with this alternative model is that known Kuparuk accumulations west of the Kuparuk Field are relatively small because the Kuparuk Formation thins to the west over the Colville High (Masterson and Paris, 1987) and there is insufficient volume in these small traps to account for the oil in place at the field. If it is argued that a deeper Ivishak accumulation was in contact with the LCU and could have spilled through the overlying Kuparuk lag sandstone interval, it must be explained why the deeper accumulation did not simply leak updip to the west through the Ivishak reservoir in response to eastward tilting (Figure 3.20). Charge of the Kuparuk Field from the underlying Shublik source interval is the simplest explanation. As discussed in Chapter 1, Kuparuk Field oils are geochemically most similar to the calcareous Shublik facies but have some geochemical characteristics that are intermediate between the predominantly shaly Shublik facies at the Prudhoe Bay Field to the east and the predominantly calcareous Shublik faces to the west at the Colville #1 and Phoenix #1 wells (Figure 1.6).

68 The EXODUS model results for the Prudhoe Bay Field fetch area imply that lack of a widespread sandstone carrier bed does not impede lateral migration for HRZ and Kingak source rocks. The Shublik source rock has an excellent carrier bed for migrated oil in the underlying Ivishak sandstone, which extends all the way to the southern portion of the study area. In contrast, the Kingak Shale has only a poor carrier bed in the underlying Sag River Sandstone that shales out at the southern boundary of the Prudhoe Bay Field (Barnes, 1987), and the HRZ Formation has no carrier bed except in the eastern part of the study area where it was deposited directly along the LCU (Figures 3.12, 3.13). EXODUS assumes that all oil expelled out of each source rock will reach the trap regardless of its carrier bed, so it might be expected that the proportion of Shublik-sourced oil at the Prudhoe Bay Field would be higher than the model predicts because of its apparently more efficient carrier system. However, the proportions of Shublik, Kingak, and HRZ co-sources at Prudhoe exactly match the model predictions (Table 3.3), so lack of a good carrier bed seems to have had little effect upon lateral migration efficiency from Kingak and HRZ sources in the Prudhoe fetch area. CONCLUSIONS 1. Burial history models predict that the first oil charge to the Prudhoe Bay Field paleostructure from Shublik, Kingak, and HRZ source rocks occurred in Late Cretaceous time when the Ivishak reservoir was buried only 2000 feet (700 meters). The presence of 25norhopanes in Prudhoe Bay main field oils suggests the possibility that this early oil charge to the Prudhoe paleo-trap was biodegraded and subsequently recharged with unaltered oil. 2. The area along the Barrow Arch east of Prudhoe Bay Field received a modeled Shublik/Kingak oil charge along the Lower Cretaceous Unconformity during Late Cretaceous time (Figure 3.16). 3. The HRZ oil charge to Prudhoe is modeled to peak in Paleocene and Eocene time. Gas charge from the Shublik Formation in the Prudhoe fetch area is modeled to begin in Late Cretaceous time and peak in Paleogene time. 4. Maximum burial depth for the fetch area south of the Prudhoe Bay Field is modeled to occur in Eocene time. The 1500C isotherm and postulated onset of CO2 generation from Lisburne Group carbonates is modeled to extend within 12 miles (20 kilometers) of the present-day southern boundary of the Prudhoe Bay Field. 5. Formation of the Prudhoe Bay Field tar mat likely began when a Paleogene gas charge arrived and began to deasphalt the accumulation, and continued as the oil-water contact swept upward through the Ivishak reservoir during post-Eocene burial, tilting, and spillage. 6. The EXODUS model predicts a mixed oil charge in the fetch area for the Prudhoe Bay Field consisting of 59% Shublik, 28% HRZ, and 13% Kingak co-sources. The isotopic

69 composition, API gravity, and sulfur content of the Prudhoe Bay main field oil accumulation closely match the oil composition predicted by EXODUS. 7. Post-Eocene eastward tilting of 10-20 reduced the hydrocarbon column at the Prudhoe Bay main field and created the structural closure at the Prudhoe Bay West End. Oil that spilled from the Prudhoe Bay main field into the overlying West Sak reservoir is modeled to have migrated west into the present-day West Sak Field. 8. Post-Eocene tilting created a north/northeast-striking fault set and re-activated older eastand northwest-striking faults. Oil from the Prudhoe Bay Ivishak sandstone is postulated to have spilled into the West Sak sandstones along east-and northwest-striking faults that connect the two reservoirs and are sub-parallel to the inferred direction of Paleogene maximum horizontal compressive stress. In contrast, only gas appears to have leaked along the north/northeast-striking faults that connect the Kuparuk and West Sak reservoirs in the Kuparuk Field area. 9. Shublik source rock is modeled to enter the oil window beneath the Kuparuk Field at the same time that the fields structural closure began to form in Eocene time. The 6 billion barrels of oil in place at Kuparuk Field match the modeled volume of expelled oil from the underlying Shublik Formation. Vertical migration of oil could have occurred along northwest-striking faults that are parallel to the inferred Paleogene direction of maximum horizontal stress and connect the Shublik source interval with the overlying Kuparuk reservoir. 10. The occurrence of mixed oils and gases in the area west of the Kuparuk Field can be explained by vertical migration of hydrocarbons from underlying Shublik and Kingak source rocks in the model. Vertical hydrocarbon migration in this area is likely enhanced by widespread faulting along the crest of the Barrow Arch. 11. The total expelled oil volume within the modeled Prudhoe Bay Field fetch area of 4,000 square miles (10,000 square kilometers) is 168 billion barrels. The estimated 40 to 50 billion barrels of original oil in place in the Prudhoe Bay and West Sak Field areas implies a Prudhoe Bay fetch area migration efficiency of 25 to 30%. 12. The relatively high migration efficiency in the Prudhoe fetch area likely reflects the fact that all three source rocks are in direct contact with the Ivishak and Sag River Sandstone reservoirs at the Prudhoe Bay Field, and that a Prudhoe paleo-trap with a large fetch area has existed since Late Cretaceous time. 13. The presence or absence of carrier beds appear to have had little effect upon the migration efficiency of oil from Shublik, Kingak, and HRZ sources in the Prudhoe fetch area. 14. Despite the many geological uncertainties and limitations of the simplified EXODUS map-based burial history model used in this study, the model nevertheless closely matches the bulk composition of a mixed Prudhoe Bay crude oil that was generated from

70 three source rocks over a time span of more than 65 million years, and provides a framework to explain the filling history of other North Slope fields.

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84
Table 1.1 Rock Eval data for source rocks Top Base Type (feet) (feet) %S TOC S1 S2 1.8 2.8 1.7 m/u m/u m/u m/u 2.0 2.0 4.9 4.3 5.4 1.7 7.0 5.9 3.9 1.6 2.8 1.7 1.3 2.8 3.3 1.6 1.9 6 39 26 35 9 53 39 24

Well Phoenix #1a Phoenix #1a Phoenix #1a Phoenix #1 Phoenix #1 Phoenix #1 Phoenix #1 PBU U-13 PBU U-13 PBU 12-03 PBU 12-03 PBU 12-03 PBU M-7 PBU M-7 PBU U-13 PBU Tract 33-11-12 Oliktok Point #1 Kalubik #1 Hemi Springs #3 Delta State #1 Badami #1 Point McIntyre #11 (P1-12) Kuukpik #3 PBU 16-11 Phoenix #1 Long Island #1
a

Zone

S3 0.67 0.89 0.89 0.46 0.35 0.27 0.42 0.9

T max m/u m/u m/u 427 420 428 427 426

HI 259 689 532 645 540 754 663 509

OI 33 18 21 9 20 4 7 23

S1/ PI TOC 0.21 0.07 0.06 0.04 0.23 0.06 0.04 0.08 0.8 0.6 0.4 0.2 1.6 0.5 0.3 0.5

Shublik A 16 core 7813 7898 Shublik B 15 core 7902 7958 Shublik C 38 core 7966 8079 Shublik A 1 core 7834 7834 Shublik B 1 core 7903 7903 Shublik B 1 core 7932 7932 Shublik C 1 core 7985 7985 Average for calcareous Shublik facies: Shublik A 6 Shublik C 6 Shublik A 2 Shublik B 2 Shublik C 3 core core core core core

11058 11091 m/u 3.35 1.3 17 0.35 438 517 10 0.09 0.4 11131 11151 m/u 2.19 0.9 9 0.33 439 367 16 0.07 0.4 9013 9032 9051 9022 9042 9074 2.0 1.2 1.3 4.5 2.3 30 0.3 1.9 2.1 11 0.2 3.4 2.3 22 0.2 430 600 15 0.15 1.0 430 588 13 0.16 1.1 430 278 11 0.15 1.0 436 587 13 0.06 0.4 436 558 17 0.06 0.3 435 470 13 0.10 0.6 444 454 18 0.04 0.2 445 318 71 0.11 0.4 439 296 21 0.19 0.7 438 412 11 0.11 0.5 441 312 34 0.16 0.6 430 428 23 0.17 0.9 431 409 8 0.11 0.5 0.3 0.8

Shublik A 2 core 9312 9320 m/u 4.0 1.6 24 0.5 Shublik B 2 core 9349 9353 m/u 2.1 0.6 12 0.4 Average for shaly Shublik facies: 1.5 3.0 1.4 16 0.3 Kingak Kingak Kingak Kingak HRZ HRZ HRZ HRZ HRZ HRZ HRZ HRZ 2 25 57 core core core 10999 11001 m/u 8.8 1.6 40 1.7 9713 8270 9761 m/u 4.1 1.3 15 2.0 8326 m/u 1.8 1.1 6 0.3

5 cuttings 7570 7620 m/u 5.0 2.4 20 0.5 Average for Kingak: 2.8 1.3 10 0.8 14 11 4 13 4 1 core core core core core core 8430 9308 8600 m/u 5.9 4.9 25 1.1 9328 m/u 3.7 1.9 15 0.3 0.3 0.5

12560 12565 m/u 2.1 1.3 7 9826 6002 9032 9907 m/u 3.3 1.4 9

433 247 17

429 271 17 0.13 0.4 429 419 23 0.06 0.2 431 147 14 0.33 0.7 423 308 26 0.10 0.3 422 286 15 0.03 0.1 430 356 17 0.14 0.6

6011 m/u 3.5 0.8 15 0.4 9032 m/u 6.0 4.4 9 7420 m/u 2.9 1.0 9 0.8 0.8

1 cuttings 7390 1 core

8000 8000 m/u 7.3 0.6 21 1.1 Average for HRZ: 4.2 2.5 16 0.6

Data from Robison and others (1996). %S=% sulfur; TOC=total organic carbon (%); S1=free hydrocarbons in rock (mg/g); S2=hydrocarbons from thermal breakdown of kerogen (mg/g); S3=CO2 from thermal breakdown of kerogen (mg/g); T max=temperature of peak S2 yield (0C); HI=S2x100/TOC; OI=S3x100/TOC; PI=S1/(S1+S2)

Well Phoenix #1 Phoenix #1 Phoenix #1 Phoenix #1 Phoenix #1

Lab Number

Zone

Table 1.2 Carbon isotope, GC, GC/MS and GC/MS/MS data for source rocks Sample Depth (feet 13Csat 13Caro Pr/ DBT/ C29H/ C23T/ H35/ % 25n/ Type MD) (PDB) (PDB) Ph Phen C30H C30H H34 C28 NDR Dino H30 -29.9 -30.1 -30.2 -30.1 -30.4 -30.1 0.2 -30.0 -30.3 -30.6 -30.5 -30.8 -29.3 -30.3 -30.3 -29.9 -30.2 0.4 -30.2 0.4 -29.4 -30.1 -30.9 -31.4 -32.1 -30.8 1.06 -29.5 -29.7 -29.9 -29.8 -29.9 -29.8 0.2 -29.6 -29.6 -29.5 -29.1 -29.9 -29.2 -29.5 -29.9 -29.4 -29.5 0.3 -29.6 0.3 -29.4 -29.6 -30.3 -31 -31.4 -30.3 0.86 1.4 1.3 1.0 1.0 1.3 1.2 0.2 2.0 1.7 1.7 1.8 1.5 1.8 1.6 0.9 1.9 1.7 0.3 0.62 0.68 0.67 0.54 0.68 0.6 0.06 0.53 0.35 0.42 0.18 0.53 0.34 0.50 0.42 0.54 0.4 0.12 1.00 0.64 0.77 0.74 0.51 0.7 0.18 0.39 0.33 0.37 0.33 0.48 0.59 0.63 0.56 0.64 0.5 0.13 0.6 0.19 0.44 0.47 0.62 0.48 0.49 0.5 0.07 0.79 0.56 0.56 0.53 0.48 0.6 0.12 0.26 0.29 0.31 0.23 0.42 0.47 0.6 0.42 0.69 0.4 0.16 1.24 0.79 1.27 1.30 1.11 1.1 0.21 0.68 0.88 0.81 0.72 0.78 0.72 0.99 1.26 1.10 0.88 0.20 25 27 25 24 25 25 1 0.11 m/u m/u m/u 0.08 0.10 0.02 0.29 m/u m/u m/u 0.23 0.26 0.04 0.02 0.01 0.01 0.01 0.01 0.01 0.004

Ts/ Tm 0.44 0.54 0.51 0.45 0.46 0.5 0.04

VR
20S

VR
MPI

97R00312 Shublik A core 7834 97R00328 Shublik B core 7933 97R00341 Shublik C core 7984 97R00342 Shublik C core 7985 97R00357 Shublik C core 8054 Average for calcareous Shublik facies: Standard deviation: 92R03711 92R03712 92R03714 92R03716 Shublik A Shublik A Shublik A Shublik A core core core core 11058 11073 11083 11091

0.7 0.8 0.8 0.8 0.7 0.7 0.03

0.8 0.8 0.8 0.8 0.7 0.8 0.02 0.7 0.6 0.7 0.7 0.8 0.8 0.8 0.8 0.8 0.7 0.1 0.7 0.1 0.7 0.7 0.7 0.7

PBU U-13 PBU U-13 PBU U-13 PBU U-13 PBU 12-3 PBU 12-3 PBU 12-3 PBU 12-3 PBU 12-3

25 m/u m/u <0.01 1.61 0.9 24 0.10 0.35 m/u 2.71 0.8 24 m/u m/u <0.01 1.59 0.8 23 0.15 0.33 m/u 1.88 0.9 25 m/u m/u 25 m/u m/u 26 m/u m/u 26 m/u m/u 26 m/u m/u 25 0.13 0.34 1 0.04 0.01 0.03 0.02 0.03 0.02 0.04 0.03 0.01 1.12 0.80 0.78 0.76 0.70 1.3 0.68 0.8 0.7 0.8 0.8 0.7 0.8 0.1

97R00372 Shublik A core 9013 97R00373 Shublik A core 9021 97R00375 Shublik B core 9041 97R00377 Shublik C core 9062 97R00378 Shublik C core 9074 Average for shaly Shublik facies: Standard deviation: Average for Shublik: Standard deviation:

1.5 0.5 0.4 0.15 1.7 0.50 2.3 0.22 1.9 0.56 2.3 0.03 1.9 0.05 2.0 0.3 0.3 0.25

0.5 0.98 25 0.11 0.30 0.01 1.0 0.8 0.16 0.23 1 0.03 0.05 0.01 0.68 0.1 0.09 0.46 23 0.09 0.33 m/u 1.14 0.6

PBU U-13 Oliktok Point #1 Kalubik #1

92R03710 92R05492 92R03627

Kingak Kingak Kingak Kingak

core core

11001 8270-8312

0.17 0.50 24 0.25 0.40 <0.01 1.00 0.6 0.32 0.85 24 0.08 0.54 23 m/u m/u m/u m/u 0.01 0.87 0.6 m/u 0.95 0.6

cuttings 7610-7620 core 8399-8405

Kuparuk State #1 96Z00002 Kuparuk 22-11-12 96Z00009

Kingak core 9390 Average for Kingak: Standard deviation:

0.07 0.59 26 m/u m/u m/u 1.26 0.6 0.7 0.1 0.59 24 0.17 0.37 <0.01 1.0 0.6 0.7 0.11 0.15 1 0.11 0.05 0.16 0.01 0.03

147

Well Hemi Springs #3 Hemi Springs #3 Hemi Springs #3 PBU 16-11 Badami #1 Delta State #1

Lab Number 92R00137 92R00138 92R00139 92R00141 94R00818 96R03796

Zone HRZ HRZ HRZ HRZ HRZ HRZ

Table 1.2 continued Sample Depth (feet 13Csat 13Caro Pr/ DBT/ C29H/ C23T/ H35/ % 25n/ Type MD) (PDB) (PDB) Ph Phen C30H C30H H34 C28 NDR Dino H30 core core core core core 8568.3 8569.5 8576.5 9032 12563 -29.8 -30.3 -29.8 -28.8 -29.6 -27.7 -27.6 -28.1 -28.4 -28.1 2.0 0.01 2.1 0.07 2.0 0.09 2.6 0.65 1.5 0.24 0.48 0.38 0.35 0.54 0.49 0.65 0.5 0.11

Ts/ Tm

VR
20S

VR
MPI

0.07 0.72 30 m/u m/u <0.01 0.92 0.6 0.07 0.56 28 0.31 0.38 <0.01 1.73 0.7 0.07 0.62 28 0.28 0.37 <0.01 1.85 0.7 0.12 0.58 29 m/u m/u <0.01 0.31 0.7

0.8 0.8 0.8 0.7 0.7

0.11 0.67 35 0.60 0.28 0.01 0.93 0.8

core 9322 -29.3 -27.9 1.0 m/u Average for HRZ: -29.6 -28.0 1.9 0.2 Standard deviation: 0.5 0.3 0.6 0.26 Depth = measured depth of core or cuttings sample 13Csat = carbon isotopic composition of saturated hydrocarbons in the C 15+ fraction

0.11 2.45 29 0.37 0.45 m/u 0.82 0.7 0.6 0.1 0.93 30 0.39 0.37 <0.01 1.1 0.7 0.7 0.02 0.75 3 0.14 0.07 0.59 0.05 0.1

13Caro = carbon isotopic composition of aromatic hydrocarbons in the C 15+ fraction Pr/Ph = pristane/phytane (saturate GC, area if available; otherwise whole oil GC, area) DBT/Phen = dibenzothiophene/phenanthrene ( m/z 191 & 184, area) Hughes et al. (1995) C29H/C30H = C29 hopane/C30 hopane (m/z 191, area) C23TT/C30H = C23 tricyclic terpane/C30 hopane (m/z 191, area) H35/H34 = H35 homohopane/H34 homohopane (m/z 191, area) %C28 = 100*C28/(C27 + C28 + C29) 14, 17() steranes (m/z 217, height) NDR = (13,17,20S-24-nordiacholestane + 13,17,20R-24-nordiacholestane)/(13,17,20S-24-nordiacholestane + 13,17,20R-24-nordiacholestane + 13,17,20S-27-nordiacholestane + 13,17,20R-27-nordiacholestane) Holba et al. (1998). Dino = 20R-dinosteranes/(20R-dinosteranes + 20R-3 -methyl-24-ethylcholestane) Moldowan et al. (1998) 25n/H30 = ratio of C29 17,25-norhopane to C30 17-hopane (m/z 191, area) Ts/Tm = C27 -18 trisnorhopane/C27 -17 trishorhopane (m/z 191, area) VR20S = inferred vitrinite reflectance of source rocks calculated as (0.5*(20S/20R C 29 steranes)) + 0.35 (Sofer, 1993; m/z 217, height) VRMPI = inferred vitrinite reflectance of source rocks calculated as (0.6*MPI-1) + 0.37 (Radke, 1988) m/u = missing or unreliable data

148

Well Kuparuk Field KRU 1D-4 KRU 1E-11 KRU 1Q-12 KRU 2A-2 KRU 2A-2 KRU 2B-5 KRU 2D-3 KRU 2E-10 KRU 2F-9 KRU 2G-10 KRU 2H-8 KRU 2T-10 KRU 2U-16 KRU 2V-3 KRU 2W-12 KRU 2W-12 KRU 2X-7 KRU 3A-16 KRU 3B-3 KRU 3C-6 KRU 3J-8 KRU 3K-11 KRU 3N-13

Lab Number

Reservoir

Table 1.3 Geochemical data for North Slope oils 13 13 Depth Oil % Csat Caro Pr/ DBT/ C29H/ C23T/ H35/ % 25n/ 0 (feet) API %S Asp ()PDB ()PDB Ph Phen C30H C30H H34 C28 NDR Dino H30 22 22 23 24 23 23 23 22 21 22 23 25 25 25 m/u 24 26 23 24 20 24 21 22 23 1.5 30 32 28 27 29 26 26 25 25 28 2.4 1.7 1.8 1.7 1.5 1.7 1.7 1.7 1.7 1.6 1.6 1.7 1.5 1.5 1.5 1.4 1.6 1.5 1.7 1.6 2 1.6 1.9 1.7 1.6 0.1 1.0 1.1 m/u m/u 0.9 m/u m/u m/u 1.1 1.0 0.1 17 26 21 21 22 24 18 21 18 8 28 7 17 23 13 19 14 32 16 21 15 14 21 19 6 -30.1 -30.1 -30.1 -30.1 -29.9 -29.9 -29.8 -29.9 -30.0 -30.1 -30.0 -30.0 -30.2 -29.9 -30.0 -30.0 -30.0 -30.1 -29.9 -30.0 -29.8 -29.9 -30.2 -30.0 0.1 -29.6 -30.0 -29.8 -29.8 -29.8 -29.9 -29.7 -29.8 -29.8 -29.8 0.1 -29.7 -29.7 -29.7 -29.5 -29.4 -29.5 -29.5 -29.6 -29.5 -29.5 -29.6 -29.5 -29.6 -29.4 -29.6 -29.5 -29.6 -29.5 -29.5 -29.6 -29.5 -29.6 -29.8 -29.6 0.1 2.0 2.1 1.7 2.1 1.7 2.0 2.2 2.0 1.7 2.0 2.1 1.8 1.8 1.9 1.8 1.7 2.0 1.8 1.6 2.0 1.5 1.8 2.0 1.9 0.2 0.68 0.71 0.74 0.60 0.59 0.58 0.61 0.61 0.58 0.58 0.66 0.74 0.64 0.58 0.72 0.72 0.63 0.81 0.74 0.72 0.76 0.78 0.70 0.67 0.07 0.70 0.67 0.56 0.63 0.74 0.63 0.32 0.67 0.64 0.62 0.12 0.84 0.88 0.88 0.85 0.86 0.82 0.84 0.84 0.83 0.85 0.85 0.83 0.84 0.84 0.86 0.88 0.85 0.90 0.87 0.92 0.89 0.91 0.86 0.86 0.03 0.54 0.54 0.52 0.54 0.52 0.53 0.55 0.52 0.55 0.53 0.01 0.68 1.2 0.59 1.2 0.69 1.1 0.57 1.2 0.60 1.2 0.55 1.1 0.57 1.1 0.56 1.1 0.55 1.3 0.56 1.2 0.57 1.1 0.54 1.0 0.60 1.3 0.54 1.2 0.69 1.2 0.67 1.3 0.61 1.2 0.68 1.2 0.70 1.2 0.65 1.3 0.76 1.3 0.64 1.2 0.59 1.1 0.62 1.2 0.06 0.08 0.28 1.2 0.33 1.1 0.31 1.2 0.33 1.2 0.33 1.2 0.28 1.1 0.33 1.2 0.31 1.2 0.33 1.2 0.31 1.2 0.02 0.04 25 24 24 24 24 24 24 24 25 24 23 24 25 24 24 23 23 23 24 24 24 23 24 24 0.6 32 33 32 31 31 31 31 31 32 32 0.7 0.15 0.16 m/u 0.17 0.16 m/u m/u m/u 0.16 m/u m/u m/u m/u m/u 0.13 0.14 m/u m/u m/u m/u m/u 0.13 m/u 0.15 0.02 0.39 0.39 0.37 0.36 0.38 0.34 0.37 0.36 0.36 0.37 0.02 0.24 0.35 m/u 0.27 0.26 m/u m/u m/u 0.35 m/u m/u m/u m/u m/u 0.28 0.28 m/u m/u m/u m/u m/u 0.20 m/u 0.28 0.05 0.38 0.44 0.40 0.37 0.38 0.41 0.37 0.37 0.34 0.38 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.02 0.03 0.03 0.02 0.03 0.03 0.03 m/u 0.04 0.03 0.004 0.05 0.05 0.04 0.05 0.05 0.05 0.04 0.05 0.05 0.05 0.004

Ts/ Tm 0.49 0.51 0.51 0.47 0.49 0.54 0.52 0.47 0.54 0.52 0.55 0.47 0.48 0.50 0.52 0.55 0.55 0.56 0.55 0.51 0.52 0.49 0.49 0.51 0.03 0.89 0.86 0.84 0.82 0.85 0.83 0.86 0.82 0.81 0.84 0.03

VR
20S

VR
MPI

Source S S S S S S S S S S S S S S S S S S S S S S S

90X02558 Kuparuk C -6395 90X02566 Kuparuk A -6328 90X02571 Kuparuk A -6120 90X02565 Kuparuk C -5851 90X02574 Kuparuk A -5934 90X02562 Kuparuk A -5928 90X02573 Kuparuk A -5912 90X02572 Kuparuk A -5950 90X02563 Kuparuk A -5873 90X02564 Kuparuk A -6001 90X02554 Kuparuk A -5990 90X02577 Kuparuk A -5910 90X02569 Kuparuk A -5808 90X02560 Kuparuk A -5832 90X02567 Kuparuk C -5795 90X02568 Kuparuk A -5963 90X02559 Kuparuk C -5737 90X02556 Kuparuk A -6157 90X02570 Kuparuk A -6137 90X02561 Kuparuk A -6626 90X02575 Kuparuk A -6199 90X02578 Kuparuk A -6745 90X02557 Kuparuk A -6398 Average for Kuparuk Field: Standard deviation:

0.8 0.7 0.8 0.7 0.7 0.7 0.8 0.7 0.7 0.7 0.8 0.7 0.7 0.7 0.8 m/u 0.8 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.03 0.7 0.7 0.7 0.7 0.7 0.7 0.8 0.8 0.7 0.7 0.02

0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.01 0.7 0.7 0.7 0.7 0.7 0.8 0.7 0.7 0.7 0.7 0.03

Prudhoe Bay Main Field - Ivishak Reservoir PBU DS 5 90X02441 Ivishak -8700 PBU 4-5 86X01787 Ivishak -8763 PBU 5-8 96X04359 Ivishak -8867 PBU 7-12 96X04397 Ivishak -8884 PBU 15-16 86X01788 Ivishak -8713 PBU 17-1 96X04417 Ivishak -8930 PBU E-5 96X04427 Ivishak -8892 PBU H-4 96X04431 Ivishak -8882 PBU N-5 96X04433 Ivishak -8856 Average for Prudhoe Bay Main Field Ivishak: Standard deviation:

2 6 8 4 15 8 7 5 7 4

-29.1 1.4 -29.3 1.3 -29.2 1.4 -29.3 1.4 -29.3 1.4 -29.5 1.4 -29.1 1.4 -29.3 1.4 -29.3 1.4 -29.3 1.4 0.1 0.03

S/H/K S/H/K S/H/K S/H/K S/H/K S/H/K S/H/K S/H/K S/H/K

149

Well

Lab Number

Reservoir

Table 1.3 continued 13 13 % Csat Caro Pr/ Depth Oil 0 (feet) API %S Asp ()PDB ()PDB Ph 25 22 25 27 27 30 26 2.7 1.2 1.1 1.0 1.0 0.8 0.6 1.0 0.2 0.2 0.4 0.3 1.4 1.4 1.2 1.3 1.3 1.2 1.2 0.3 0.3 0.3 0.3 1.0 1.1 1.0 1.0 0.2 0.1 0.4 1.5 1.7 0.2 0.7 15 33 15 17 13 12 18 8 5 2 4 9 11 9 13 12 12 11 1 2 2 2 5 3 9 9 6 2 2 8 8 2 1 -30.1 -29.9 -30.2 -30.0 -30.5 -30.7 -30.2 0.3 -31.3 -31.2 -31 -30.0 -30.0 -29.9 -29.9 -29.9 -29.9 -29.9 -31.1 -30.9 -31.0 -31.0 -29.3 -29.5 -29.9 -29.6 -32.7 -28.6 -28.6 -30.2 -30.2 -29.1 -29.5 -29.6 -29.4 -29.6 -29.5 -29.6 -30.1 -29.6 0.2 -30.6 -30.3 -30 -29.4 -29.5 -29.5 -29.5 -29.5 -29.4 -29.5 -30.3 -30.1 -30.2 -30.2 -28.8 -29.0 -29.5 -29.1 -31.0 -27.3 -28.1 -29.6 -29.7 -28.2 -29.2 1.5 1.5 1.6 1.4 1.5 1.6 1.5 0.1 1.5 1.7 1.6 m/u m/u m/u m/u m/u m/u

DBT/ C29H/ C23T/ H35/ % 25n/ Phen C30H C30H H34 C28 NDR Dino H30 m/u m/u m/u m/u 0.26 0.39 0.33 0.09 0.12 m/u 0.12 0.26 0.54 0.51 m/u m/u m/u 0.5 0.15 0.18 0.23 0.2 0.65 0.71 0.51 0.6 0.12 0.12 0.15 0.72 0.67 0.07 0.76 0.51 0.56 0.52 0.52 0.50 0.47 0.51 0.03 0.36 0.43 0.40 0.55 0.57 0.53 0.54 0.54 0.53 0.5 0.44 0.42 0.45 0.4 0.58 0.59 0.53 0.6 0.40 0.49 0.39 0.87 0.85 0.37 0.84 0.45 1.1 0.38 1.1 0.46 1.1 0.38 1.1 0.38 1.0 0.46 1.0 0.42 1.1 0.04 0.05 0.34 0.46 0.40 0.40 0.42 0.40 0.38 0.36 0.36 0.4 0.14 0.12 0.16 0.14 0.39 0.34 0.40 0.38 0.07 0.10 0.15 0.68 0.65 0.08 6.50 0.7 0.9 0.8 1.1 1.0 1.1 1.1 1.0 1.0 1.1 0.6 0.6 0.7 0.7 1.2 1.2 1.1 1.2 0.5 0.5 1.0 1.2 1.2 1.0 1.4 30 30 28 29 29 27 29 1.2 0.33 0.34 m/u 0.30 0.23 0.23 0.29 0.05 0.40 0.30 m/u 0.33 0.30 0.29 0.32 0.05 0.05 m/u 0.04 0.05 0.04 0.03 0.04 0.01

Ts/ Tm 0.79 1.06 0.88 0.88 1.00 1.00 0.94 0.10

VR
20S

VR
MPI

Source S/K/H S/K/H S/K/H S/K/H S/K/H S/K/H

Prudhoe Bay Field West End Hurl St. #1 94X03658 Ivishak -8899 SE Eileen #2 86X00030 Ivishak -8892 Kuparuk St. 7-11-12 94X03665 Ivishak -8842 Kuparuk St. #1 94X03689 Ivishak -8876 Kuparuk St. 33-11-12 94X03690 Ivishak -8930 W Kuparuk 3-11-11 94X03662 Ivishak -8895 Average for PBU West End Ivishak: Standard deviation: W Kuparuk 3-11-11 Socal 33-29E

0.8 0.7 0.8 0.8 0.8 0.8 0.8 0.02

m/u m/u m/u m/u 0.7 0.7 0.7 0.00

94X03692 Sag -8720 36 96X04440 Sag -8647 35 Average for PBU West End Sag: 36 17 17.9 21.2 17.4 18.3 20.3 21 39 35 37 37 27 27 28 28 36 36 22 23 22 38 36

25 0.16 0.28 <0.01 2.20 0.8 0.7 25 0.14 0.26 m/u 1.66 0.8 m/u 25 0.15 0.27 1.9 0.8 0.7 32 32 33 31 31 31 32 0.39 0.37 0.38 0.38 0.36 0.36 0.37 0.39 0.40 0.41 0.38 0.42 0.43 0.42 0.11 0.10 0.09 0.12 0.08 0.08 0.1 0.84 0.83 0.84 0.80 0.84 0.85 0.8

K/S K/S

West Sak Field Oils West Sak 1-01 93X03317 West Sak D -3484 West Sak 1-01 93X03316 West Sak B -3543 West Sak 1-01 93X03315 West Sak A -3748 WSP 8I 86X01803 West Sak D -3389 WSP 8I 86X01802 West Sak B/A -3470 WSP 8I 86X01801 West Sak A -3563 Average for West Sak Zone A Oils: Alpine Field Oils Bergschrund #1 Alpine #1 Fiord #3 94X03608 Alpine -6863 95X03808 Alpine -7128 95X03815 Alpine -6695 Average for Alpine Field Oils:

0.7 0.8 S/H/K 0.7 0.8 S/H/K 0.7 0.8 S/H/K 0.7 m/u S/H/K 0.7 m/u S/H/K 0.7 m/u S/H/K 0.7 0.8 0.7 0.8 0.7 0.7 0.8 0.8 0.8 0.8 0.7 0.7 0.8 0.8 0.7 0.7 0.8 0.8 0.8 0.7 0.8 K K K

2.1 2.1 2.2 2.1 1.4 1.4 m/u 1.4 2.4 2.2 1.6 1.5 1.8 1.7 1.2

27 0.13 0.22 <0.01 1.37 27 0.14 0.33 0.02 1.30 27 m/u m/u <0.01 1.21 27 0.14 0.28 0.02 1.3 33 32 33 27 23 28 34 25 24 34 27 0.38 0.40 0.38 0.39 0.15 0.44 0.55 0.12 0.13 0.44 m/u 0.28 0.31 0.41 0.30 0.25 0.24 0.36 0.28 0.27 0.36 m/u

Point McIntyre Field Oils Pt. McIntyre 5 (P1-25) 90X02461 Kuparuk -8770 Pt. McIntyre 6 (P2-58) 90X02443 Kuparuk -8988 P1-07 97X05173 Kuparuk -8692 Average for Pt. McIntyre Field Oils: Other North Slope Oils Kavearak Point 95X03855 Umiat #4 86X01911 Kuukpik #3 93X03284 Kuukpik #3 93X03283 Kuukpik #3 93X03282 Tarn #2 97X04690 Colville #1 94X03557 Jurassic Cretaceous Cretaceous Kuparuk Jurassic Cretaceous Shublik -7669 184 -2666 -6210 -6343 -5175 -7847

0.05 0.87 0.8 0.06 0.83 0.7 0.09 0.84 0.7 0.07 0.8 0.7 <0.01 m/u 0.02 0.02 0.02 0.01 <0.01 1.00 0.67 1.16 0.52 0.53 1.30 7.60 0.8 0.7 0.7 0.7 0.7 0.8 0.8

S/H/K S/H/K S/H/K

K H H S S H S

150

Well

Lab Number

Reservoir

Table 1.3 continued 13 13 Depth Oil % Csat Caro Pr/ 0 (feet) API %S Asp ()PDB ()PDB Ph

DBT/ C29H/ C23T/ H35/ % 25n/ Phen C30H C30H H34 C28 NDR Dino H30 0.37 0.05 0.42 0.05 0.24 0.02 0.48 0.01 0.32 0.01 0.33 <0.01 0.24 <0.01 m/u <0.01 <0.01 m/u

Ts/ Tm 0.65 0.81 0.82 0.77 0.84 0.67 0.49 0.62 53.8

VR
20S

VR
MPI

Source S/H/K S/H K/S S/K K/S S/K S/K S L

W Kuparuk 3-11-11 94X03660 Kuparuk -6539 27 1.3 m/u -30.0 -29.6 1.7 0.46 0.69 0.62 1.1 28 0.29 N Kuparuk 26-12-12 94X03666 Kuparuk -6775 27 1.1 11 -29.5 -28.9 1.5 0.61 0.55 0.42 1.2 31 0.36 N Kuparuk 26-12-12 94X03667 Sag -8767 32 0.7 5 -30.8 -30.1 1.6 0.37 0.59 0.72 1.1 24 0.20 Temptation #1 96X04458 Kuparuk -7147 29 1.0 6 -30.7 -30.2 1.9 0.37 0.64 0.47 0.9 26 0.14 Temptation #1 96X04459 Jurassic -7378 30 0.9 6 -31.2 -31.0 2.0 0.32 0.58 0.31 0.8 26 0.14 Fiord #1 92X03043 Kuparuk -6651 31 0.9 2 -30.7 -29.9 2.1 0.40 0.67 0.46 1.2 24 0.18 Fiord #1 92X03042 Jurassic -7061 27 1.2 7 -30.4 -29.7 2.0 0.51 0.81 0.64 1.2 24 0.15 Kalubik #1 93X03259 Kuparuk -6378 26 1.4 23 -30.0 -29.4 1.4 0.76 0.86 0.85 1.3 25 m/u KRU 2F-20 97X07026 Lisburne -8989 33 0.7 1 -29.4 -28.6 1.2 3.20 4.29 36.00 m/u 32 0.12 Depth = average depth of tested interval, feet subsea %Asp = % asphaltenes in oil Source interpretations for oils are S = Shublik, K = Kingak, H = HRZ, and L = Lisburne. The origin of gas is not addressed in this table. m/u = missing or unreliable data Other abbreviations are the same as in Table 1.2

0.7 0.8 0.8 0.8 0.8 0.8 0.7 0.7 0.7

0.8 0.7 0.7 0.8 0.8 0.8 0.8 0.8 0.9

151

90
Table 1.4 Average concentrations of biomarkers in core extracts (ppm) Shublik Shublik Shaly Kingak Shale Mature Facies (Prudhoe Bay Calcareous Calcareous (Prudhoe Bay Field, Kalubik Facies Shublik Field) #1) (Phoenix #1) (Colville #1) 326 689 4,423 6,901 1,100 1,383 1,967 741 857 0.7 0.70% 193 192 3,381 8,578 420 504 1,028 307 290 0.5 0.64% 203 199 3,745 9,016 184 580 1,112 384 243 0.5 0.69% 82 33 467 674 388 94 126 43 73 0.7 1.04%

Biomarker C27 18(H)-trisnorhopane (Ts) C27 17(H)-trisnorhopane (Tm) Dibenzothiophene (DBT) Phenanthrene C23 tricyclic terpane C29 hopane C30 hopane C34 homohopane C35 homohopane C29/C30 hopane Vitrinite reflectance (% Ro)

Well Reservoir Prudhoe Main Field Ivishak gas cap (10) Prudhoe West End* Ivishak gas cap (1) Kuparuk Field Kuparuk solution gas (3) Kalubik #1 Kuparuk solution gas (1) Point McIntyre Field Kuparuk solution gas (3) West Sak Field West Sak solution gas (3) Alpine Field Alpine solution gas (1) Tarn #2 Bermuda solution gas (1) Umiat #8 Cretaceous wellhead (1) Prudhoe Lisburne Pool Lisburne solution gas (2) KRU 2F-20 Lisburne well test (1)
13

Table 1.5 Average chemical and isotopic compositions of selected North Slope gases n -Butane Type of Methane Ethane Propane 13 13 13 13 C D C C Sample (#) mole% mole% mole% C mole% -39.1 -38.2 -42.9 -41.1 -40.4 -49.0 -56.3 -47.4 -41.3 m/u -36.2 -189 m/u -179 -179 -192 -304 -227 -202 -168 m/u -160 78.1 m/u 82.7 85.0 81.2 98.7 74.7 79.0 97.3 m/u 78.6 -29.1 -34.4 -32.0 -34.7 -29.0 -27.5 -35.4 -34.3 -31.4 m/u -30.0 5.6 m/u 7.8 7.2 7.7 0.4 10.1 9.3 1.9 m/u 1.0 -29.7 -33.8 -31.2 -33.6 -29.1 -27.2 -33.2 -33.1 -29.3 m/u -29.0 2.4 m/u 4.7 3.8 3.4 0.1 9.3 6.9 0.2 m/u 0.2 -30.4 -32.8 -31.1 m/u m/u -28.6 -33.1 m/u m/u m/u -28.9 0.6 m/u 1.5 1.1 0.9 0.1 2.3 2.0 0.1 m/u 0.1

i -C4/ Carbon Dioxide Isobutane 13 13 C mole% n -C4b C mole% -29.3 0.27 0.4 -5.1 11.0 m/u m/u m/u m/u m/u m/u 0.77 0.5 -17.8 0.7 m/u 0.51 0.5 -18.9 0.9 m/u 0.42 0.5 -14.9 5.1 -28.9 0.07 0.8 13.8 0.4 -33.2 1.19 0.5 m/u 0.6 m/u 0.81 0.4 m/u 0.2 m/u 0.03 0.2 m/u 0.1 m/u m/u m/u -3.2 14.0 m/u 0.05 0.6 -0.8 17.3

C values are per mil PDB; D values are per mil SMOW *Chung et al., 1988 The number of samples appear in parenthesis after the sample type. m/u = missing or unreliable data n -C4=n -butane; i -C4=isobutane

92

Table 2.1 West Sak, Kuparuk, and Prudhoe Bay Field oils analyzed by GC/IRMS Oil Depth Gravity (0 API) Unita Well Reservoir (feet) Lab # Field 17.40 86X1803 West Sak KRU WSP 8I West Sak D 3468-3524 18.30 86X1802 West Sak KRU WSP 8I West Sak B, A4 3543-3611 0 20.3 86X1801 West Sak KRU WSP 8I West Sak A3 3632-3708 93X3317 West Sak KRU 93X3316 West Sak KRU 93X3315 West Sak KRU 90X2566 90X2558 90X2567 90X2568 94X3660 Kuparuk Kuparuk Kuparuk Kuparuk Prudhoe KRU KRU KRU KRU West Sak 1-01 West Sak 1-01 West Sak 1-01 1E-11 1D-04 2W-12 2W-12 West Sak D West Sak B West Sak A Kuparuk A Kuparuk C Kuparuk C Kuparuk A Kuparuk C 3579-3613 3644-3666 3686-4034 6328 6395 5795 5963 6599-6619 17 17.90 21.20 220 0 22 m/u 240 270
0

%S 1.3 1.3 1.2 1.4 1.4 1.2 1.8 1.7 1.4 1.6 1.3 0.6 1.1 m/u

Topping Loss 14% 16% 19% 11% 16% 23% 16% 19% 11% 15% 33% 35% 32% m/u

PBU W Kuparuk 3-11-11

300 94X3662 Prudhoe PBU W Kuparuk 3-11-11 Ivishak 8960-8970 320 86X1787 Prudhoe PBU 4-05 Ivishak 9865-9972 0 24 96X4417 Prudhoe PBU 17-01 Ivishak 9272-9300 a KRU = Kuparuk River Unit, PBU = Prudhoe Bay Unit %S = per cent sulfur in whole oil 0 Topping loss is per cent of whole oil under a stream of nitrogen at 40 C for one hour. m/u = missing or unreliable data

93
Table 2.2 GC/IRMS carbon isotopic compositions of selected C6 and C7 compounds in oils Well WSP 8I Reservoir MCP West Sak D C () (n=3)
13

Carbon Isotopic Composition Bz CH 3MH n -C7 MCH

Tol

-27.2 -30.1 -26.4 -28.9 -30.2 -27.0 -29.0 0.40 0.77 0.30 0.12 0.31 0.21 0.20 -28.5 -29.4 -26.7 -30.3 -30.4 -27.7 -29.1 0.26 0.10 0.22 0.17 0.27 0.24 0.20 -28.9 -30.2 -27.2 -30.4 -31.0 -28.0 -29.1 0.26 0.19 0.13 0.15 0.24 0.34 0.33 -29.5 -30.8 -29.2 -31.7 -33.6 -30.3 -30.6 0.21 0.57 0.08 0.06 0.21 0.28 0.27 -27.8 -29.2 -28.1 -29.5 -30.4 -27.5 -29.6 0.10 0.19 0.07 0.26 0.23 0.06 0.30 -27.5 -27.5 -27.2 -30.2 -29.1 -26.7 -29.2 0.36 0.17 0.15 0.17 0.27 0.09 0.18 -29.2 -30.4 -29.3 -32.2 -33.5 -30.0 -30.2 0.10 0.64 0.17 0.13 0.36 0.22 0.10 -29.1 -30.1 -28.9 -31.1 -33.1 -29.8 -30.0 0.40 0.09 0.18 0.40 0.27 0.12 0.20 -28.9 -29.6 -28.3 -31.4 -32.9 -30.0 -30.1 0.79 0.18 0.54 0.49 0.06 0.07 0.09 -29.8 -30.1 -29.9 -31.7 -33.3 -30.1 -30.3 0.15 0.26 0.32 0.06 0.19 0.11 0.21 -29.6 -30.6 -30.2 -31.8 -33.4 -30.7 -30.4 0.31 0.29 0.72 0.38 0.30 0.07 0.31 -29.4 -30.2 -29.0 -31.8 -32.5 -29.9 -30.5 0.12 0.39 0.32 0.12 0.29 0.21 0.20 -31.0 -29.1 -30.8 -32.5 -33.9 -31.8 -30.3 0.21 0.25 0.15 0.05 0.12 0.35 0.11 -28.6 -28.1 -28.3 -30.2 -30.5 -29.0 -28.4 0.35 0.03 0.20 0.55 0.19 0.48 0.10

WSP 8I

West Sak B/A4

C () (n=3)
13

WSP 8I

West Sak B/A4 (duplicate) West Sak A3

C () (n=3)
13

WSP 8I

C () (n=3)
13

West Sak 1-01

West Sak D

C () (n=3)
13

West Sak 1-01

West Sak B

C () (n=3)
13

West Sak 1-01

West Sak A

C () (n=3)
13

KRU 1E-11

Kuparuk A

C () (n=3)
13

KRU 1D-04

Kuparuk C

C () (n=3)
13

KRU 2W-12

Kuparuk C

C () (n=3)
13

KRU 2W-12

Kuparuk A

C () (n=3)
13

PBU W Kuparuk 3-11-11

Kuparuk C

C () (n=3)
13

PBU W Kuparuk 3-11-11

Ivishak

C () (n=3)
13

PBU 4-05

Ivishak

C () (n=3)
13 13

C () -30.8 -29.8 -30.9 -32.7 -34.1 -31.5 -31.4 (n=4) 0.13 0.25 0.05 0.19 0.15 0.14 0.36 Average for all oils 0.28 0.29 0.24 0.22 0.23 0.20 0.21 a MCP=methylcyclopentane, Bz=benzene, CH=cyclohexane, 3MH=3-methylhexane, n -C7=heptane, MCH=methylcyclohexane, Tol=toluene is calculated from repeated analyses (either 3 or 4) of the same sample PBU 17-01 Ivishak

94

Table 2.3 Concentrations of selected C6 and C7 compounds in West Sak and Kuparuk oils Well Reservoir Concentration (parts per thousand) MCP Bz CH 3MH n -C7 MCH Tol MN WSP 8I WSP 8I WSP 8I West Sak D West Sak B/A4 West Sak A3 0.22 0.56 3.14 0.34 0.44 0.55 0.41 0.92 3.54 0.76 1.00 1.17 0.35 0.68 1.67 0.70 1.35 7.46 1.06 1.82 2.21 1.69 3.69 3.18

West Sak 1-01 West Sak 1-01 West Sak 1-01

West Sak D West Sak B West Sak A

0.31 0.47 1.63

0.41 0.59 0.49

0.70 0.91 2.38

0.49 0.86 1.19

0.35 0.58 1.87

1.10 1.33 7.21

1.17 1.96 2.63

1.71 3.11 4.20

KRU 1E-11 Kuparuk A 2.08 0.75 2.32 1.42 3.21 5.56 2.34 2.44 MN = 1-methylnaphthalene + 2-methylnaphthalene. See Table 2.2 for other abbreviations.

95
Table 2.4 Condensate-range maturity parameters in West Sak and Prudhoe Bay oils Field West Sak West Sak West Sak West Sak West Sak West Sak Prudhoe Bay Prudhoe Bay Well WSP 8I WSP 8I WSP 8I West Sak 1-01 West Sak 1-01 West Sak 1-01 W Kuparuk 3-11-11 4-05 Reservoir West Sak D West Sak B, A4 West Sak A3 West Sak D West Sak B West Sak A Ivishak Ivishak Heptane Value 8 10 8 9 9 10 22 21 Isoheptane Value 0.5 1.0 1.0 0.9 0.9 0.6 0.9 1.0

Prudhoe Bay 17-01 Ivishak 20 0.9 Heptane Value = (n -heptane x 100)/( cyclohexane through methylcyclohexane, excluding 1, cis-2-dimethylcyclopentane) (Thompson,1979) Isoheptane Value = (methylcyclohexanes (2- & 3-))/(dimethylcyclopentanes (1c3-, 1t3-, & 1t2-)) (Thompson, 1979)

96

Table 2.5 Data from Kuparuk Field bottomhole oil samples n -Heptane/ Toluene/ Lab # Group 1 90X2554 90X2560 90X2562 90X2563 90X2564 90X2565 90X2572 90X2574 90X2577 Group 2 90X2556 90X2567 90X2568 90X2570 90X2571 90X2575 90X2557 90X2558 90X2561 90X2578 90X2559 90X2569 90X2573 90X2566 Well KRU 2H-08 KRU 2V-03 KRU 2B-05 KRU 2F-09 KRU 2G-10 KRU 2A-02 KRU 2E-10 KRU 2A-02 KRU 2T-10 Reservoir Kuparuk A Kuparuk A Kuparuk A Kuparuk A Kuparuk A Kuparuk C Kuparuk A Kuparuk A Kuparuk A Depth n -Heptane Methylcyclohexane 5990 5832 5928 5873 6001 5851 5950 5934 5910 1.36 1.14 1.23 1.26 1.29 1.28 1.31 1.47 1.29 0.41 0.46 0.43 0.43 0.41 0.43 0.49 0.39 0.42

Topping Loss 18% 23% 24% 16% 22% 26% 11% 19% 10%

0.71 0.58 20% 0.74 0.59 11% 0.77 0.57 15% 0.75 0.57 10% 0.73 0.58 14% 0.70 0.57 10% 0.77 0.54 25% 0.80 0.52 19% 0.77 0.53 8% 0.81 0.51 9% 0.90 0.54 22% 0.92 0.52 12% 0.98 0.51 13% 0.92 0.51 16% Average Topping Loss 16% Depths are feet subsea at the midpoint of the tested interval 0 Topping loss is per cent of whole oil removed under a stream of nitrogen at 40 C for one hour and is a gravimetric measure of the C15- fraction of an oil

KRU 3A-16 KRU 2W-12 KRU 2W-12 KRU 3B-03 KRU 1Q-12 KRU 3J-08 KRU 3N-13 KRU 1D-04 KRU 3C-06 KRU 3K-11 KRU 2X-07 KRU 2U-16 KRU 2D-03 KRU 1E-11

Kuparuk A Kuparuk C Kuparuk A Kuparuk A Kuparuk A Kuparuk A Kuparuk A Kuparuk C Kuparuk A Kuparuk A Kuparuk C Kuparuk A Kuparuk A Kuparuk A

6157 5795 5963 6137 6120 6199 6398 6395 6626 6745 5737 5808 5912 6328

97

Table 2.6 Calculation of inferred isotopic fractionation factor between Kuparuk residual oil and West Sak secondary gas/condensate charge Inferred Residual Oil Migrant Gas Kuparuk Zone C 1D-04 a C() -29.6 -28.3 -31.4 -32.9
13

West Sak Zone A

Between West Sak Condensate and

WS 1-01 Kuparuk Residual Oil 13 b 13 C() C() (gas/liquid) Compound Benzene -30.4 0.7 0.99924 Cyclohexane -29.3 1.0 0.99901 3-Methylhexane -32.2 0.8 0.99919 Heptane -33.5 0.6 0.99933 Average 0.8 0.99919 a Average of 1D-04 triplicate analyses b Average of WS 1-01 triplicate analyses

Table 3.1 Source rock geochemical parameters used in EXODUS model Shublik Shublik Calcareous Shaly Formation Facies Facies Kingak HRZ S2 (mg/g) 24 10 10 16 TOC (%) 4 3 3 4 Density (g/cc) 2.6 2.6 2.5 2.4 S2 = hydrocarbons from thermal breakdown of kerogen TOC = total organic carbon (%)

98
Table 3.2 Kinetic parameters for source rocks Shublik Shublik Shublik Kingak 97R00331 93R01144 97R00378 92R03710 PBU U-13 (Term Well Phoenix #1 PBU M-07 PBU 12-03 B) core core core core 7946 9312 9074 11001 7835 8535 8772 8680 90 105 100 105 105 115 105 115 0.70 m/u 0.64 0.73

Formation Sample number

Kingak 92R03625

HRZ 92R00137 Hemi Springs #3 core 8568 8450 m/u 110 0.7

HRZ 92R05496

Well Sample Type Measured Depth Subsea Depth 0 a Present-day Temperature ( C) 0 b Maximum Temperature ( C) c R0 (%)
0 d

Kalubik #1 cuttings 7590-7600 7553-7563 90 105 0.78

Phoenix #1 cuttings 7390-7420 7279-7309 80 95 0.6 422 m/u 0.2 12.82E+13

Rock Eval T max ( C) 426 436 430 440 438 429 % Sulfur 2.0 m/u 1.5 m/u m/u m/u Thiophene ratio 0.2 0.2 m/u 0.1 0.1 0.3 Discrete distribution -1 Frequency Factor (A; sec ) 1.338E+13 4.35E+13 7.6304E+13 26.33E+13 11.48E+13 8.46E+13 Activation Energy (E; kcal/mole) 43 0.05 44 0.18 0.10 45 1.13 0.20 46 0.26 0.42 47 2.10 48 49 50 51 85.59 52 0.13 53 12.55 83.52 63.76 77.83 54 13.52 0.02 55 1.13 6.22 16.63 79.08 19.16 56 4.54 93.39 57 4.73 10.96 1.93 58 1.90 0.48 59 0.02 4.58 60 2.05 0.23 0.38 61 0.34 62 63 0.60 8.06 64 0.20 65 2.03 Gaussian distribution -1 A (sec ) 7.17E+12 2.00E+13 E principal (kcal/mole) 50.098 52.456 (cal/mole) 220 73 a Temperatures are estimated from production temperatures,bottomhole temperature surveys or drill stem tests. b Maximum temperatures are estimated from 1D GENESIS burial history models. c Ro is mean random vitrinite reflectance in oil. Values are averages of intervals within 150 feet of the sample.
d

0.84 0.39 0.41 1.71

5.11 36.22 27.17 11.86 9.11 1.82 3.09

2.27

T max is the average value for the source interval. Thiophene ratio = 2,3-dimethylthiophene/(1,2-dimethylbenzene + n -non-1-ene); Tegelaar and Noble (1993). m/u = missing or unreliable data

Table 3.3 Comparison of EXODUS model predictions with Prudhoe Bay main field oil compositions EXODUS Model 13 13 Oils Prediction Csat Caro API Gravity % Sulfur Kingak-Sourced Oil (Alpine Field) HRZ-Sourced Oil (Tarn #2 well) Shublik-Sourced Oil (Kuparuk Field) -31 -29.1 -30 -30.2 -28.2 -29.6 37 38 23 0.3 0.2 1.6 13% Co-source 28% Co-source 59% Co-source

Prudhoe Bay Main Field Oil -29.8 -29.3 29 1.0 EXODUS Prediction for Prudhoe Trap -29.9 -29.3 29.0 1.0 13 Csat = carbon isotopic composition of saturated hydrocarbons in the C15+ fraction Caro = carbon isotopic composition of aromatic hydrocarbons in the C15+ fraction
13

168 Billion Barrels

161

162

Figure 1.1. Location of oil fields on the North Slope of Alaska.

163 Figure 1.2. Generalized structural cross section from the Brooks Range across the North Slope to the Beaufort Sea. The line of cross section is shown on Figure 1.1. Modified from Bird and Bader (1987).

164

Figure 1.3. Generalized stratigraphic column for the Prudhoe Bay/Kuparuk River area of the Alaskan North Slope.

165

Figure 1.4. Structural cross section through Kuparuk, West Sak, and Prudhoe Bay Fields. The line of cross section is shown on Figure 1.1.

104

Figure 1.5. Wireline log response and organic richness of source intervals in the HRZ Formation, Kingak Shale, and Shublik Formation. The locations of the Fiord #1 and Kalubik #1 wells are shown on Figure 1.6.

167

Figure 1.6. Locations of oil samples, source rock samples, and producing units.

168

Figure 1.7. Rock Eval data from Shublik, Kingak, and HRZ cores. S2 is the generative potential and TOC is the weight per cent of total organic carbon. The hydrogen index (HI) is defined as S2/TOC*100. Well names and depths are shown in Table 1.1.

Figure 1.8. GC/MS saturate fraction mass chromatogram (m/z 191) of source rock extracts and oils sourced from the Kingak Shale and from shaly and calcareous facies of the Shublik Formation. Sample locations are shown on Figure 1.6. TT23 = C23 tricyclic terpane, TS = C27 18(H)-trisnorneohopane, TM = C27 17(H)-trisnorhopane, H29 = C29 hopane, H30 = C30 hopane, H34 = C34 homohopane, H35 = C35 homohopane.

169

1.2
Average Kuparuk Field Oil

170

Average Shublik Calcareous Source Rock Average Prudhoe Bay Main Field Oil Average Shublik Shaly Source Rock Average HRZ Source Rock

0.8 Compound Ratio

0.6

Average Kingak Source Rock

0.4

0.2

0 DBT/Phen C29H/C30H C23T/C30H H35/H34 % C28 NDR Dino

Source-Diagnostic Compounds

Figure 1.9. Source-diagnostic compounds in Kuparuk and Prudhoe Bay Field oils compared to Shublik, Kingak, and HRZ source intervals. Kuparuk Field oils are interpreted as sourced from the Shublik Formation, and Prudhoe Bay main field oils are interpreted as co-sourced from all three source rocks. Abbreviations for compound names are listed in Table 1.3.

171 167 Figure 1.10. Carbon isotopic composition of saturated and aromatic compounds extracted from cores through the Shublik, Kingak, and HRZ source intervals. Well names and depths are shown in Table 1.2.

Figure 1.11. GC/MS/MS saturate fraction mass chromatogram (m/z 358 217 transition) of HRZ, Kingak, and Shublik source rocks and oils from Prudhoe Bay, West Sak, and Tarn Fields. All three oils contain relatively high concentrations of 24-norcholestane and are interpreted to have been sourced or co-sourced by the HRZ Formation.

172

173

Figure 1.12. Carbon isotopic composition of saturated and aromatic compounds in crude oils. Well names and depths are shown in Table 1.3. The outlines of source rock isotopic compositions are taken from Figure 1.10.

1 0.9 0.8 0.7


Average Shublik Source Rock

Average Prudhoe West End Sag Oil

Average Kingak Source Rock

Compound Ratio

0.6 0.5

Average Alpine Field Oils

Kavearak Point Oil

0.4 0.3 0.2 0.1 0 DBT/Phen C29H/C30H C23T/C30H H35/H34 % C28 NDR Dino

Source-Diagnostic Compounds

Figure 1.13. Source-diagnostic compounds in Kingak-sourced oils compared to Shublik and Kingak source rocks. Kavearak Point and Alpine Field oils are sourced from the Kingak Shale, and Prudhoe Bay West End oils are co-sourced from the Shublik and Kingak intervals. Abbreviations are listed in Table 1.3.

174

45 Shublik-sourced oils Alpine Field oils Mixed Kingak/Shublik sources 40 High-maturity Shublik oil Bergschrund 1 Fiord 3 Sinclair Colville #1 35 Alpine 1 Fiord 1 (Kuparuk) 30 Temptation 1 (Jurassic) Kavearak Point oil Prudhoe West End Sag oils

Oil Gravity (degrees API)

Nechelik Core Predicted 0 Oil Gravity: 29 API


25

Temptation 1 (Kuparuk)

Fiord 1 (Jurassic) Kalubik 1 (Kuparuk) Kuukpik 3 (Kuparuk) Kuukpik 3 (Jurassic)

KRU 1D-4 20

15 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

C29/C30 Hopane Ratio (m/z 191, area)


Figure 1.14. Prediction of API gravity from biomarker ratios in oils sourced from the Shublik Formation and the Kingak Shale in the Colville Delta area. An oil gravity of 200 API is predicted for a Jurassic reservoir in the Nechelik well, which was not tested. The Sinclair Colville oil was generated at late oil window maturity (Ro 1%).

175

1.2

Umiat #4 Oil
1

Kuukpik #3 Oil

0.8 Compound Ratios

Tarn #2 Oil

Average HRZ Source Rock


0.6

0.4

0.2

0 DBT/Phen C29H/C30H C23T/C30H H35/H34 % C28 NDR Dino

Source-Diagnostic Compounds

Figure 1.15. Source-diagnostic compounds in Umiat, Tarn, and Kuukpik #3 oils. Kuukpik #3 and Tarn Field oils are interpreted as sourced from the HRZ Formation, and Umiat #4 oil is interpreted as sourced from either the Torok Formation (Magoon and Bird, 1985) or from a different facies of the HRZ Formation. Abbreviations are in Table 1.3.

176

2.5

Shublik-Sourced Oils

Kuparuk Field Kalubik #1

West Sak Field Prudhoe Main Field Ivishak Prudhoe West End Ivishak Kavearak Point #1 Tarn #2 Fiord #1

1.5

Biodegraded West Sak oils

Sulfur (%)
1

Alpine Field
HRZ and KingakSourced Oils

0.5

Mixed Oils

0 10 15 20 25 30 35 40 45

Oil Gravity (degrees API)

Figure 1.16. API gravity and sulfur content of oils in the study area. Shublik-sourced oils have high sulfur concentrations and medium API gravities, whereas HRZ and Kingak-sourced oils have low sulfur concentrations and high API gravities.

177

0.60 Kuukpik #3

Prudhoe Bay Main Field oils Prudhoe West End Ivishak oils

0.50 N Kuparuk 26-12-12 Kuparuk oil Tarn #2 0.40


Kuparuk Field oils Prudhoe West End Sag oils

Shublik/Kingak/HRZ Mixtures
Kingak-sourced oil

NDR Ratio

0.30 Kavearak Point Kingak-sourced oil 0.20


HRZ-sourced oils

W Kuparuk 3-11-11 Kuparuk oil N Kuparuk 26-12-12 Kuparuk oil

0.10

N Kuparuk 26-12-12 Sag oil Prudhoe Main Field gas cap

0.00 -31.5

-31

-30.5

-30

-29.5

-29

-28.5

-28

-27.5

C15+ 13C aromatic hydrocarbons ( PDB)

Figure 1.17. Biomarker and isotopic evidence for mixed oils in the Prudhoe/Kuparuk area. Oils with a NDR ratio (Holba et al., 1998) greater than 0.2 are interpreted as having a HRZ source or co-source.

178

179 Figure 1.18. Carbon isotopic composition of saturated and aromatic compounds extracted from Ivishak Sandstone cores in the Prudhoe Bay Field. Prudhoe oils are interpreted as co-sourced from Shublik, HRZ, and Kingak intervals (see also Figure 1.12).

118

Figure 1.19. Evidence for gravity segregation in the Prudhoe Bay main field oil column above the tar mat.

119

Figure 1.20. Concentration and isotopic composition of carbon dioxide in separator gas from the Pt. McIntyre Field. The southeastward increase in carbon dioxide concentration could be due to diffusion of isotopically heavy CO2 from the Ivishak or Lisburne pools at the Prudhoe Bay Field.

120

Figure 1.21. Whole oil gas chromatograms (GC) and GC/MS saturate fraction mass chromatograms (m/z 191) of oils from the Kalubik #1 and the West Sak, Kuparuk, and Prudhoe Bay Fields. The West Sak Field oil is biodegraded and is interpreted to have spilled from the Prudhoe Bay Field. The Prudhoe Bay and Kuparuk Fields contain elevated concentrations of 25-norhopanes that suggest an episode of biodegradation that was followed by recharge of unaltered oil. ISTD = internal standard, MCH = methylcyclohexane, NC8 = octane, 25norH = C29 17,25-norhopane. Other abbreviations are the same as on Figure 1.8. Well locations are shown on Figure 1.6.

0 -25

0.2

0.4

1/Cn

0.6

0.8

-30

-35
13 C ( PDB)

Interpreted Range of Pristine Shublik-Sourced Gas

-40

-45

-50

-55

West Sak Field KRU 2F-20 Lisburne Prudhoe Bay Main Field Prudhoe Bay West End Kuparuk Field Kalubik #1 Kuparuk Tarn #2 Alpine Field Point McIntyre Field n -Butane Propane Ethane Methane

-60

Figure 1.22. Natural gas plot (Chung et al., 1988) showing carbon isotopic compositions of gases and interpreted range of Shubliksourced gases. West Sak Field gas is biodegraded, and Alpine and Tarn Field gases are interpreted as a mixture of biogenic methane and Shublik-sourced gas.

183

Figure 1.23. Wetness and methane carbon isotopic composition of gases interpreted as sourced from the Shublik Formation (Kalubik #1) and the Lisburne Formation (2F-20). Well locations are shown on Figure 1.6. Modified from Tissot and Welte (1984).

184

123

Figure 1.24. Carbon and hydrogen isotopic compositions of methane from the Kalubik #1 and 2F-20 wells. The 2F-20 gas plots as more thermally mature than the Kalubik #1 gas on both this figure and on Figures 1.23 and 1.25. Modified from Schoell (1983).

186

Figure 1.25. Maturity of gases in the Kalubik #1 and 2F-20 wells, using the method of James (1990).

20 18

Separator Gas Carbon Dioxide (mole %)

16 14 12 10 8 6 4 2 0 -20

KRU 2F-20 Lisburne Gas Prudhoe Lisburne Pool Prudhoe Bay Main Field Pt. McIntyre Field Kuparuk Field
-18 -16 -14 -12 -10 -8 -6 -4 -2 0

13C of Carbon Dioxide in Separator Gas ( PDB)

Figure 1.26. Average concentration and carbon isotopic composition of carbon dioxide in gases. All gases are interpreted to fall along a mixing line between Shublik-sourced gas at the Kuparuk Field and Lisburne-sourced gas tested from the 2F-20 well.

187

Figure 2.1. Locations of oil samples, source rock samples, and north/northeast-striking faults of Tertiary age that displace the top of the Kuparuk River Formation. Some north/northeast-striking faults connect the Kuparuk and West Sak reservoirs in the vicinity of the West Sak 1-01 and WSP 8I wells. Faults outside of the Kuparuk River Unit area are not shown. Cross section A-A appears on Figure 2.2. Locations of additional oil and source rock samples are shown on Figures 1.1 and 2.14.

188

Figure 2.2. Schematic structural cross section illustrating filling history of West Sak Field. Oil from the Prudhoe trap spilled vertically into the West Sak sands and laterally into the West Sak Field during a Tertiary tilting event on the North Slope, and was moderately biodegraded. The Kuparuk Field filled separately, and subsequently lost gas by the process of evaporative fractionation. Kuparuk Field gas and condensate leaked up faults to the overlying West Sak Field and was then lightly biodegraded in the shallowest West Sak reservoirs. Modified from Carman and Hardwick (1983).

189

Figure 2.3. GC/IRMS whole oil mass chromatogram (m/z 44) of Kuparuk zone A oil from the KRU 1E-11 well. MCP = methylcyclopentane, BZ = benzene, CH = cyclohexane, 3MH = 3-methylhexane, NC7 = heptane, MCP = methylcyclohexane, TOL = toluene.

190

129

Figure 2.4. GC/MS saturate fraction mass chromatogram (m/z 191) of extracts from Shublik, Kingak, and HRZ source rocks. Well locations are shown on Figures 1.1 and 2.1. TT23 = C23 tricyclic terpane, TS = C27 18(H)-trisnorneohopane, TM = C27 17(H)-trisnorhopane, H29 = C29 hopane, H30 = C30 hopane.

130

Figure 2.5. Whole oil gas chromatograms (a, b, and c) and GC/MS saturate fraction mass chromatograms (m/z 191; d, e, and f) of oils from the West Sak, Kuparuk, and Prudhoe Bay Fields. Sample locations are shown on Figure 2.1. Note that West Sak oil is anomalously enriched in gasoline-range compounds that should not be present in a moderately biodegraded oil. Also note the very similar biomarker fingerprints in Prudhoe Bay and West Sak oils. ISTD = internal standard, MCH = methylcyclohexane, NC8 = octane, MN = 1- and 2-methylnaphthalene. Other abbreviations are the same as on Figure 2.4.

Figure 2.6. The isotopic compositions of West Sak methane, carbon dioxide, and formation water suggest that methane was generated by CO2 reduction in an anaerobic environment. After Whiticar et al. (1986).

0 -25

0.2

0.4

1/Cn

0.6

0.8

194

-30

Biodegradation

West Sak Field Solution Gas

13 C ( PDB)

-35

Kuparuk Field Solution Gas

-40

Biogenic methane

-45

-50
n -Butane Propane Ethane Methane

Figure 2.7. Carbon isotopic compositions of solution gas from West Sak and Kuparuk Fields. West Sak Field solution gas is interpreted as biodegraded, based upon its dryness (> 98% methane), high isobutane/n-butane ratio, isotopically heavy carbon dioxide and isotopically light methane, and propane that is isotopically heavier than either ethane or butane.

Figure 2.8. Wireline logs and whole oil gas chromatograms from the West Sak reservoir at the WSP 8I well. Reservoir sandstones are highlighted with stipple pattern. Oil viscosities are average values (centipoise) for zones A, B, and D at the drill site. The highest oil gravities and lowest viscosities are found in the deepest West Sak reservoirs in zone A. Topping loss is a measure of the C15- fraction of the oil and is determined gravimetrically. IC5 = 2-methylbutane, MCH = methylcyclohexane, MN = 1- and 2methylnaphthalene.

195

Concentration (parts per thousand)

7 6 5 4 3 2 1 0 MCP Benzene Cyclohexane 3MHexane Heptane MCH Toluene 1MN + 2MN

Biodegradation

Compound
8I zone A3 1-01 zone B 8I zone B,A4 1-01 zone D 8I zone D 1E-11 Kuparuk 1-01 zone A

196

Figure 2.9. Concentrations of selected compounds in oils from West Sak and Kuparuk Fields. Oils in both fields have relatively high concentrations of methylcyclopentane (MCP), cyclohexane, and methylcyclohexane (MCH).

135
-25 -26 -27 -28

13 C ( PDB)

-29 -30 -31 -32 -33 -34

a. WSP 8I West Sak Oils


-35

MCP

Benzene

Cyclohexane

3MHexane

Heptane

MCH

Toluene

Compound
WSP 8I Zone A3 WSP 8I Zone B/A4 WSP 8I Zone B/A4 (duplicate) WSP 8I Zone D

-25 -26 -27 -28

13 C ( PDB)

-29 -30 -31 -32 -33 -34

b. WS 1-01 West Sak Oils


-35

MCP

Benzene

Cyclohexane

3MHexane

Heptane

MCH

Toluene

Compound
WS1-1 Zone A WS1-1 Zone B WS1-1 Zone D

Figure 2.10. Carbon isotopic composition of oils from the West Sak reservoir in the WSP 8I well (a) and the WS 1-01 well (b). Error bars represent one standard deviation based upon triplicate analyses. MCP = methylcyclopentane, 3MHexane = 3-methylhexane, MCH = methylcyclohexane.

-25 -26 -27 -28

13 C ( PDB)

-29 -30 -31

Biodegradation

-32 -33 -34 -35

MCP

Benzene

Cyclohexane

3MHexane

Heptane

MCH

Toluene

Compound
WSP 8I Zone A3 West Sak 1-01 Zone A WSP 8I Zone B/A4 Average West Sak 1-01 Zone B

Figure 2.11. Carbon isotopic composition of West Sak oils in zones A and B. The isotopic compositions in zone A oils are nearly identical, suggesting a common origin of the migrant gas/condensate before biodegradation in the shallower zone B reservoir. Abbreviations are on Figure 2.10.

198

137

Figure 2.12. Wireline logs and permeabilities measured from cores through the West Sak reservoir in the WS 1-01 well. The permeability of Zone B is higher than Zone D, which could account for the heavier isotopic composition and interpreted increased biodegradation of zone B C6 and C7 compounds relative to the shallower zone D.

138
-28

-29

13 C ( PDB)

-30

-31

-32

-33

a. West Sak and Kuparuk Oils


-34

MCP

Benzene

Cyclohexane

3MHexane

Heptane

MCH

Toluene

Compound
WSP 8I Zone A3 KRU 1D-04 C Kuparuk PBU W KUP 3-11-11 Kuparuk West Sak 1-01 Zone A KRU 2W-12 C Kuparuk KRU 1E-11 A Kuparuk KRU 2W-12 A Kuparuk

-28

-29

-30

13 C ( PDB)

-31

Increased proportion of HRZ-sourced oil

-32

-33

-34

b. West Sak and Ivishak Oils


-35

MCP

Benzene

Cyclohexane

3MHexane

Heptane

MCH

Toluene

Compound
WSP 8I Zone A3 PBU DS 4-05 Ivishak WS 1-01 Zone A PBU 17-01 Ivishak PBU W KUP 3-11-11 Ivishak

Figure 2.13. Comparison of carbon isotopic compositions in West Sak zone A and Kuparuk oils (a) and Prudhoe Ivishak oils (b). The West Sak zone A oils fall within the same range and match the isotopic pattern of the Kuparuk oils. Abbreviations are on Figure 2.10.

Figure 2.14. Evidence for evaporative fractionation in Kuparuk Field oils and simplified structure map (feet subsea) on the top of Unit A, Kuparuk Formation. Group 1 oils are located near the crest of the Kuparuk Field and have experienced more evaporative fractionation, as measured by Thompson parameters of toluene/heptane and heptane/methylcyclohexane, than Group 2 Kuparuk oils. 1E-11 and 1D-04 oils have experienced more evaporative fractionation than 2W-12 oils, and are isotopically heavier (see Figure 2.13).

201

Log [ n -Alkane Molar Fraction]

-1

KRU 1E-11 Kuparuk oil PBU 4-5 Ivishak oil PBU W Kup 3-11-11 Ivishak oil Linear regression for 1E-11 oil -2 C8 C10 C12 C14 C16 C18 C20 C22 Carbon Number
202

R2 = 0.99

Figure 2.15. Comparison of n-alkane molar fractions in Kuparuk and Prudhoe Bay Field oils. The Kuparuk 1E-11 oil is not significantly depleted in light n-alkanes relative to Prudhoe Bay oils, and there is no evidence for significant gas stripping of Kuparuk oil.

203

Figure 3.1. Location of modeled wells on the North Slope of Alaska.

142

Figure 3.2. Burial history model of the Phoenix #1 well. Vitrinite reflectances were calculated with the Lawrence Livermore National Lab (LLNL) kinetic model (Burnham and Sweeney, 1989). A heat flow of 1.3 Heat Flow Units (HFU) was used in all modeled wells.

143

Figure 3.3. Burial history model of the Bush Federal #1 well. Tertiary uplift of 4500 feet was calculated by calibration of the models with measured vitrinite reflectances. Note that surface temperature is modeled to vary with time and that the Late Cretaceous surface temperatures are modeled to be about 200C warmer than today.

144

Figure 3.4. Isopach and structure maps used in the EXODUS model. The top Kuparuk structure map was used to model the HRZ Formation, and the top Sag structure map was used to model the Kingak Shale and Shublik Formation.

20 HRZ 18 Kingak Shublik

16

S1 (mg hydrocarbons/g rock)

14

12
Hemi Springs #3

10

0 0 2 4 6 8 10 12 14 16

TOC (%)

207

Figure 3.5. Rock Eval S1 and TOC (total organic carbon) measurements on cores from HRZ, Kingak, and Shublik source rocks. Oil expulsion occurs in the EXODUS model at S1/TOC > 1 (~ 0.7 in the subsurface).

146

Figure 3.6. Isopach maps of HRZ, Kingak, and Shublik source rocks.

209

Figure 3.7. Temperature gradient across Prudhoe Bay main field at 8800 feet subsea depth.

210

460

450

Phoenix #1 (Shublik) PBU M-07 (Shublik) PBU 12-03 (Shublik) PBU U-13 (Kingak and Shublik) Kalubik #1 (Kingak) Hemi Springs #3 (HRZ) Phoenix #1 (HRZ)

T max (0C)

440

430

420

Im m at ur e ( 0. 2- 0. 6% VRe) 410 0 0. 1

Ear l y M at ur e ( 0. 6- 0. 8% VRe) 0. 2

M i ddl e M at ur e ( 0. 8- 1. 0% VRe) 0. 3

Lat e M at ur e ( 1. 0- 1. 3% VRe) 0. 4

Production Index (S1/(S1 + S2))

Figure 3.8. Rock Eval Tmax and Production Index (S1/(S1 + S2)) measurements on source rock cores.

211

Figure 3.9. Comparison between modeled and measured vitrinite reflectances. Modeled Shublik vitrinite reflectances are calculated from the LLNL Ro model (Burnham and Sweeney, 1989).

Calculated LLNL Ro (%) at Heating Rate of 1 C/my


0.6 1 0.9 0.7 0.8 0.9 1.0 1.5 2.0

Kerogen Transformation Ratio (%)

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 100 Shublik Phoenix #1 0.50C/my 10C/my

110

120

130

140

150

160
0

170

180

190

200

Temperature ( C)
Kingak Kalubik #1 (Gaussian) HRZ Hemi Springs #3 Shublik 12-03 (Shaly) Kingak Kalubik #1 HRZ Phoenix #1 Shublik Phoenix #1 (Calcareous) Kingak Term Well B Shublik M-7 (Shaly) Shublik Phoenix #1 0.5 degrees C/my

Figure 3.10. Modeled source rock transformation ratios as a function of temperature at a heating rate of 10C/my. The Gaussian kinetic model for the Kingak Shale results in a 100C reduction in the temperature required for onset of hydrocarbon generation.

212

151

Figure 3.11. Modeled rate of hydrocarbon generation from calcareous facies of the Shublik Formation at the Bush Federal #1 well. Significant amounts of gas begin to be generated at a vitrinite reflectance of 1.2%, which is the modeled maturity of the Shublik Formation beneath the Tarn and Alpine Fields.

214

Figure 3.12. Reconstructed structural cross section through Kuparuk and Prudhoe Bay Fields during development of the Lower Cretaceous Unconformity (LCU) in Early Cretaceous time (125 Ma). The line of cross section is shown on Figure 3.1.

215

Figure 3.13. Reconstructed structural cross section through Kuparuk and Prudhoe Bay Fields during Late Cretaceous time (66 Ma). Oil generated from Shublik, Kingak, and HRZ source rocks downdip in the Colville Trough has migrated into the paleostructural closures at the Prudhoe Bay Field. The line of cross section is shown on Figure 3.1.

154

Figure 3.14. Distribution of subsurface faults mapped from seismic data in the Prudhoe Bay/Kuparuk Field area. Faults that cut the top Kuparuk Formation east of the Kuparuk Field are not shown.

155

Figure 3.15. Isopach maps of Paleocene and Maastrichtian/Campanian sediments. The direction of maximum horizontal stress in the Prudhoe/Kuparuk subsurface is postulated to have shifted from north-south during Late Cretaceous time to northwest-southeast during Paleocene time in response to changes in the position of thrusting and uplift in the Brooks Range.

156

Figure 3.16. EXODUS models of hydrocarbon kitchens in Late Cretaceous time (66 Ma). The Shublik and Kingak migration pathways are modeled along the top Sag River Sandstone paleo-structural horizon, and the HRZ migration pathways are modeled along the top Kuparuk horizon.

219

Figure 3.17. Reconstructed structural cross section through Kuparuk and Prudhoe Bay Fields during Late Eocene time (40 Ma), after the onset of Tertiary uplift and eastward tilting. The Kuparuk Field closure has started to form, and Shublik source rock is modeled to be within the oil window beneath the field. The line of cross section is shown on Figure 3.1.

158

Figure 3.18. EXODUS models of hydrocarbon kitchens in Middle Eocene time (45 Ma). The structural closure at the Kuparuk Field has started to form, and the Shublik Formation is modeled to have expelled 6 billion barrels of oil directly beneath the field.

221

Figure 3.19. EXODUS modeled area of CO2 generation from the Lisburne Group in Middle Eocene time (45 Ma). The 2F-20 well tested a gas with 17% CO2 from the Lisburne Group.

160

Figure 3.20. EXODUS models of present-day hydrocarbon kitchens. The positions of the oil and gas windows correspond to the maximum temperatures experienced by the source rocks and have not been "rolled back" to account for cooling associated with uplift.

VITA Wilmer Dallam Masterson IV was born in Dallas, Texas, on July 4, 1957, the son of Dorothy Kathleen Masterson and Wilmer Dallam Masterson III. After graduating from Highland Park High School, Dallas, Texas, in 1975, he was a Clark Foundation Fellowship summer student at The University of Texas at Dallas and entered Yale University at New Haven, Connecticut in the fall. He received the degree of Bachelor of Science with a major in geology and geophysics from Yale University in May 1979. He entered the Graduate School of The University of Texas at Austin in 1979 and received the degree of Master of Arts in Geology in December, 1981. He began employment as a petroleum geologist with the Atlantic Richfield Company (ARCO) in 1981 and transferred to Anchorage, Alaska in December 1981. In 1982, he married Coleen Gayle Stone of Anchorage. Six children were born between 1987 and 1999: Wilmer Dallam V, Joseph Douglas, Kathleen Joan-Marie, Anthony Kelly, James Regan, and Mark Fitzpatrick. In 1994, he transferred to the ARCO Exploration and Technology Company in Plano, Texas and became the Director of Petroleum Systems Research. While working at ARCO, he entered the Graduate School of The University of Texas at Dallas in 1995. He transferred back to Anchorage as an Exploration Manager for ARCO Alaska, Inc., in 1997. In 2000, ARCO Alaska was acquired by Phillips Petroleum Company and became Phillips Alaska, Inc.